Co-reporter:Jiwen Jian, Qingnan Zhang, Xuan Wu, and Mingfei Zhou
The Journal of Physical Chemistry A October 19, 2017 Volume 121(Issue 41) pp:7861-7861
Publication Date(Web):October 3, 2017
DOI:10.1021/acs.jpca.7b08586
The reactions of early lanthanide metal atoms (Ce, Pr, and Nd) with carbon monoxide and nitric oxide mixtures are studied by infrared absorption spectroscopy in solid argon. The reaction intermediates and products are identified via isotopic substitution as well as theoretical frequency calculations. The results show that the reactions proceed with the initial formation of inserted NLnO molecules, which subsequently react with CO to form the NLnO(CO) complexes on annealing. The NLnO(CO) complexes further isomerize to the more stable isocyanate OLnNCO species under UV light excitation.
Co-reporter:Jiaye Jin, Lili Zhao, Xiaonan Wu, Wei Li, Yuhong Liu, Diego M. Andrada, Mingfei Zhou, and Gernot Frenking
The Journal of Physical Chemistry A April 20, 2017 Volume 121(Issue 15) pp:2903-2903
Publication Date(Web):March 27, 2017
DOI:10.1021/acs.jpca.7b00739
The carbon suboxide cation C3O2+ and the protonated carbon suboxide HC3O2+/DC3O2+ were produced in the gas phase. The vibrational spectra were measured via infrared photodissociation spectroscopy of their argon- or CO-tagged complexes. Spectroscopic evidence combined with state-of-the-art quantum chemical calculations indicate that both cations have a bent C2v symmetry and can be designated as dicarbonyls of a carbon cation and methylidyne cation, respectively.
Co-reporter:Hui Qu, Fanchen Kong, Guanjun Wang, and Mingfei Zhou
The Journal of Physical Chemistry A 2017 Volume 121(Issue 8) pp:
Publication Date(Web):February 10, 2017
DOI:10.1021/acs.jpca.6b13025
Fe–Zn and Co–Zn heteronuclear carbonyl cation complexes are produced via a laser vaporization supersonic cluster source in the gas phase. The dinuclear FeZn(CO)5+ and CoZn(CO)7+ cation complexes are observed to be the most intense heterodinuclear carbonyl cation species in the mass spectra. The infrared spectra are obtained via mass selection and infrared photodissociation spectroscopy in the carbonyl stretching frequency region. Their geometric and electronic structures are assigned with the support of density functional calculations. The FeZn(CO)5+ complex is determined to have a (OC)5Fe–Zn structure with a Fe–Zn half bond. The CoZn(CO)7+ ion is established to have a staggered (OC)4Co–Zn(CO)3 structure involving a Co–Zn σ single bond.
Co-reporter:Dr. Chaoxian Chi;Dr. Jia-Qi Wang;Hui Qu;Wan-Lu Li;Dr. Luyan Meng; Mingbiao Luo; Dr. Jun Li; Dr. Mingfei Zhou
Angewandte Chemie 2017 Volume 129(Issue 24) pp:7036-7040
Publication Date(Web):2017/06/06
DOI:10.1002/ange.201703525
AbstractWe report the preparation of UFe(CO)3− and OUFe(CO)3− complexes using a laser-vaporization supersonic ion source in the gas phase. These compounds were mass-selected and characterized by infrared photodissociation spectroscopy and state-of-the-art quantum chemical studies. There are unprecedented triple bonds between U 6d/5f and Fe 3d orbitals, featuring one covalent σ bond and two Fe-to-U dative π bonds in both complexes. The uranium and iron elements are found to exist in unique formal U(I or III) and Fe(−II) oxidation states, respectively. These findings suggest that there may exist a whole family of stable df–d multiple-bonded f-element-transition-metal compounds that have not been fully recognized to date.
Co-reporter:Dr. Chaoxian Chi;Dr. Jia-Qi Wang;Hui Qu;Wan-Lu Li;Dr. Luyan Meng; Mingbiao Luo; Dr. Jun Li; Dr. Mingfei Zhou
Angewandte Chemie International Edition 2017 Volume 56(Issue 24) pp:6932-6936
Publication Date(Web):2017/06/06
DOI:10.1002/anie.201703525
AbstractWe report the preparation of UFe(CO)3− and OUFe(CO)3− complexes using a laser-vaporization supersonic ion source in the gas phase. These compounds were mass-selected and characterized by infrared photodissociation spectroscopy and state-of-the-art quantum chemical studies. There are unprecedented triple bonds between U 6d/5f and Fe 3d orbitals, featuring one covalent σ bond and two Fe-to-U dative π bonds in both complexes. The uranium and iron elements are found to exist in unique formal U(I or III) and Fe(−II) oxidation states, respectively. These findings suggest that there may exist a whole family of stable df–d multiple-bonded f-element-transition-metal compounds that have not been fully recognized to date.
Co-reporter:Dr. Chaoxian Chi;Hui Qu;Dr. Luyan Meng;Fanchen Kong; Mingbiao Luo; Dr. Mingfei Zhou
Angewandte Chemie International Edition 2017 Volume 56(Issue 45) pp:14096-14101
Publication Date(Web):2017/11/06
DOI:10.1002/anie.201707898
AbstractInfrared photodissociation spectroscopy of mass-selected heteronuclear cluster anions in the form of OMFe(CO)5− (M=Sc, Y, La) indicates that all these anions involve an 18-electron [Fe(CO)4]2− building block that is bonded with the M center through two bridged carbonyl ligands. The OLaFe(CO)5− anion is determined to be a CO-tagged complex involving a [Fe(CO)4]2−[LaO]+ anion core. In contrast, the OYFe(CO)5− anion is characterized to have a [Fe(CO)4]2−[Y(η2-CO2)]+ structure involving a side-on bonded CO2 ligand. The CO-tagged complex and the [Fe(CO)4]2−[Sc(η2-CO2)]+ isomer co-exist for the OScFe(CO)5− anion. These observations indicate that both the ScO+ and YO+ cations supported on [Fe(CO)4]2− are able to oxidize CO to CO2. Theoretical analyses show that [Fe(CO)4]2− coordination significantly weakens the MO+ bond and decreases the energy gap of the interacting valence orbitals between MO+ and CO, leading to the CO oxidation reactions being both thermodynamically exothermic and kinetically facile.
Co-reporter:Jiwen Jian;Wei Li;Xuan Wu
Chemical Science (2010-Present) 2017 vol. 8(Issue 6) pp:4443-4449
Publication Date(Web):2017/05/30
DOI:10.1039/C7SC01399J
The organo-boron species formed from the reactions of boron atoms with acetylene in solid neon are investigated using matrix isolation infrared spectroscopy with isotopic substitutions as well as quantum chemical calculations. Besides the previously reported single C–H bond activation species, a cyclic-HBC2BH diboron species is formed via double C–H bond activation of acetylene. It is characterized to have a closed-shell singlet ground state with planar D2h symmetry. Bonding analysis indicates that it is a doubly aromatic species involving two delocalized σ electrons and two delocalized π electrons. This finding reveals the very first example of double C–H bond activation of acetylene in forming new organo-boron compounds.
Co-reporter:Shu-Xian Hu;Jiwen Jian;Jing Su;Xuan Wu;Jun Li
Chemical Science (2010-Present) 2017 vol. 8(Issue 5) pp:4035-4043
Publication Date(Web):2017/05/03
DOI:10.1039/C7SC00710H
The neutral molecule NPrO and its anion NPrO− are produced via co-condensation of laser-ablated praseodymium atoms with nitric oxide in a solid neon matrix. Combined infrared spectroscopy and state-of-the-art quantum chemical calculations confirm that both species are pentavalent praseodymium nitride-oxides with linear structures that contain PrN triple bonds and PrO double bonds. Electronic structure studies show that the neutral NPrO molecule features a 4f0 electron configuration and a Pr(V) oxidation state similar to that of the isoelectronic PrO2+ ion, while its NPrO− anion possesses a 4f1 electron configuration and a Pr(IV) oxidation state. The neutral NPrO molecule is thus a rare lanthanide nitride-oxide species with a Pr(V) oxidation state, which follows the recent identification of the first Pr(V) oxidation state in the PrO2+ and PrO4 complexes (Angew. Chem. Int. Ed., 2016, 55, 6896). This finding indicates that lanthanide compounds with oxidation states of higher than +IV are richer in chemistry than previously recognized.
Co-reporter:Jiaye Jin;Wei Li;Yuhong Liu;Guanjun Wang
Chemical Science (2010-Present) 2017 vol. 8(Issue 9) pp:6594-6600
Publication Date(Web):2017/08/21
DOI:10.1039/C7SC02472J
The cation complexes [ArB3O4]+, [ArB3O5]+, [ArB4O6]+ and [ArB5O7]+ were prepared via a laser vaporization supersonic ion source in the gas phase. Their vibrational spectra were measured via mass-selected infrared photodissociation spectroscopy. Spectroscopy combined with quantum chemical calculations revealed that the [ArB3O5]+, [ArB4O6]+ and [ArB5O7]+ cation complexes have planar structures each involving an aromatic boroxol ring and an argon–boron covalent bond. In contrast, the [ArB3O4]+ cation is characterized to be a weakly bound complex with a B3O4+ chain structure.
Co-reporter:Jiaye Jin; Guanjun Wang; Mingfei Zhou;Dr. Diego M. Andrada;Dr. Markus Hermann; Gernot Frenking
Angewandte Chemie International Edition 2016 Volume 55( Issue 6) pp:2078-2082
Publication Date(Web):
DOI:10.1002/anie.201509826
Abstract
We report the spectroscopic identification of the [B3(NN)3]+ and [B3(CO)3]+ complexes, which feature the smallest π-aromatic system B3+. A quantum chemical bonding analysis shows that the adducts are mainly stabilized by L[B3L2]+ σ-donation.
Co-reporter:Qingnan Zhang;Dr. Shu-Xian Hu;Hui Qu;Dr. Jing Su;Dr. Guanjun Wang;Jun-Bo Lu;Dr. Mohua Chen;Dr. Mingfei Zhou;Dr. Jun Li
Angewandte Chemie International Edition 2016 Volume 55( Issue 24) pp:6896-6900
Publication Date(Web):
DOI:10.1002/anie.201602196
Abstract
The chemistry of lanthanides (Ln=La–Lu) is dominated by the low-valent +3 or +2 oxidation state because of the chemical inertness of the valence 4f electrons. The highest known oxidation state of the whole lanthanide series is +4 for Ce, Pr, Nd, Tb, and Dy. We report the formation of the lanthanide oxide species PrO4 and PrO2+ complexes in the gas phase and in a solid noble-gas matrix. Combined infrared spectroscopic and advanced quantum chemistry studies show that these species have the unprecedented PrV oxidation state, thus demonstrating that the pentavalent state is viable for lanthanide elements in a suitable coordination environment.
Co-reporter:Jiwen Jian;Dr. Hailu Lin; Mingbiao Luo;Dr. Mohua Chen; Mingfei Zhou
Angewandte Chemie International Edition 2016 Volume 55( Issue 29) pp:8371-8374
Publication Date(Web):
DOI:10.1002/anie.201603345
Abstract
A ground-state boron atom inserts into the C=C bond of ethylene to spontaneously form the allene-like compound H2CBCH2 on annealing in solid neon. This compound can further isomerize to the propyne-like HCBCH3 isomer under UV light excitation. The observation of this unique spontaneous C=C bond insertion reaction is consistent with theoretical predictions that the reaction is thermodynamically exothermic and kinetically facile. This work demonstrates that the stronger C=C bond, rather than the less inert C−H bond, can be broken to form organoboron species from the reaction of a boron atom with ethylene even at cryogenic temperatures.
Co-reporter:Qingnan Zhang;Dr. Paul Jerabek; Mohua Chen; Mingfei Zhou; Gernot Frenking
Angewandte Chemie International Edition 2016 Volume 55( Issue 36) pp:10863-10867
Publication Date(Web):
DOI:10.1002/anie.201606154
Abstract
Two novel isomers of BeO4 with the structures OBeOOO and OBe(O3) in the electronic triplet state have been prepared as well as the known disuperoxide complex Be(O2)2 in solid noble-gas matrices. We also report the synthesis of the oxygen-rich bis(ozonide) complex Be(O3)2 in the triplet state which has a D2d equilibrium geometry. The molecular structures were identified by infrared absorption spectroscopy with isotopic substitutions as well as quantum chemical calculations.
Co-reporter:Jiaye Jin; Guanjun Wang; Mingfei Zhou;Dr. Diego M. Andrada;Dr. Markus Hermann; Gernot Frenking
Angewandte Chemie 2016 Volume 128( Issue 6) pp:2118-2122
Publication Date(Web):
DOI:10.1002/ange.201509826
Abstract
We report the spectroscopic identification of the [B3(NN)3]+ and [B3(CO)3]+ complexes, which feature the smallest π-aromatic system B3+. A quantum chemical bonding analysis shows that the adducts are mainly stabilized by L[B3L2]+ σ-donation.
Co-reporter:Jiwen Jian;Dr. Hailu Lin; Mingbiao Luo;Dr. Mohua Chen; Mingfei Zhou
Angewandte Chemie 2016 Volume 128( Issue 29) pp:8511-8514
Publication Date(Web):
DOI:10.1002/ange.201603345
Abstract
A ground-state boron atom inserts into the C=C bond of ethylene to spontaneously form the allene-like compound H2CBCH2 on annealing in solid neon. This compound can further isomerize to the propyne-like HCBCH3 isomer under UV light excitation. The observation of this unique spontaneous C=C bond insertion reaction is consistent with theoretical predictions that the reaction is thermodynamically exothermic and kinetically facile. This work demonstrates that the stronger C=C bond, rather than the less inert C−H bond, can be broken to form organoboron species from the reaction of a boron atom with ethylene even at cryogenic temperatures.
Co-reporter:Qingnan Zhang;Dr. Paul Jerabek; Mohua Chen; Mingfei Zhou; Gernot Frenking
Angewandte Chemie 2016 Volume 128( Issue 36) pp:11021-11025
Publication Date(Web):
DOI:10.1002/ange.201606154
Abstract
Two novel isomers of BeO4 with the structures OBeOOO and OBe(O3) in the electronic triplet state have been prepared as well as the known disuperoxide complex Be(O2)2 in solid noble-gas matrices. We also report the synthesis of the oxygen-rich bis(ozonide) complex Be(O3)2 in the triplet state which has a D2d equilibrium geometry. The molecular structures were identified by infrared absorption spectroscopy with isotopic substitutions as well as quantum chemical calculations.
Co-reporter:Qingnan Zhang;Dr. Shu-Xian Hu;Hui Qu;Dr. Jing Su;Dr. Guanjun Wang;Jun-Bo Lu;Dr. Mohua Chen;Dr. Mingfei Zhou;Dr. Jun Li
Angewandte Chemie 2016 Volume 128( Issue 24) pp:7010-7014
Publication Date(Web):
DOI:10.1002/ange.201602196
Abstract
The chemistry of lanthanides (Ln=La–Lu) is dominated by the low-valent +3 or +2 oxidation state because of the chemical inertness of the valence 4f electrons. The highest known oxidation state of the whole lanthanide series is +4 for Ce, Pr, Nd, Tb, and Dy. We report the formation of the lanthanide oxide species PrO4 and PrO2+ complexes in the gas phase and in a solid noble-gas matrix. Combined infrared spectroscopic and advanced quantum chemistry studies show that these species have the unprecedented PrV oxidation state, thus demonstrating that the pentavalent state is viable for lanthanide elements in a suitable coordination environment.
Co-reporter:Hui Qu, Guanjun Wang, and Mingfei Zhou
The Journal of Physical Chemistry A 2016 Volume 120(Issue 12) pp:1978-1984
Publication Date(Web):March 8, 2016
DOI:10.1021/acs.jpca.5b12716
Infrared photodissociation spectra are measured for mass-selected cation complexes with a chemical formula [MC7O6]+ (M = Fe, Co, Ni) formed via pulsed laser evaporation of metal target in expansions of helium gas seeded by CO. The geometries of the complexes are determined by comparison of the experimental spectra with the simulated spectra from density functional calculations. All of these complexes are identified to have [M(CO)4(C3O2)]+ structures involving a carbon suboxide ligand, which binds the metal center in an η1 fashion. The antisymmetric CO stretching vibration of C3O2 is slightly red-shifted upon coordination. The donor–acceptor bonding interactions between C3O2 and the metal centers are analyzed using the EDA-NOCV method. The results show that M ← C3O2 σ donation is stronger than the M → C3O2 π back-donation in these cation complexes.
Co-reporter:Jing Su;Shuxian Hu;Wei Huang;Jun Li
Science China Chemistry 2016 Volume 59( Issue 4) pp:442-451
Publication Date(Web):2016 April
DOI:10.1007/s11426-015-5481-z
Relativistic quantum chemistry investigations are carried out to tackle the puzzling oxidation state problem in a series of MO3- trioxide anions of all d- and f-block elements with five valence electrons. We have shown here that while the oxidation states of V, Nb, Ta, Db, Pa are, as usual, all +V with divalent oxygen O(-II) in MO3- anions, the lanthanide elements Pr and Gd cannot adopt such high +V oxidation state in similar trioxide anions. Instead, lanthanide element Gd retains its usual +III oxidation state, while Pr retains a +IV oxidation state, thus forcing oxygen into a non-innocent ligand with an uncommon monovalent radical (O•) of oxidation state -I. A unique Pr• - •(O)3 biradical with highly delocalized unpairing electron density on Pr(IV) and three O atoms is found to be responsible for stabilizing the monovalent-oxygen species in PrO3- ion, while GdO3- ion is in fact an OGd+(O22- ) complex with Gd(III). These results show that a naïve assignment of oxidation state of a chemical element without electronic structure analysis can lead to erroneous conclusions.
Co-reporter:Xiaohua Zhang;Yuzhuo Wang;Lili Hu;Dan Guo
Journal of The American Society for Mass Spectrometry 2016 Volume 27( Issue 7) pp:1256-1262
Publication Date(Web):2016 July
DOI:10.1007/s13361-016-1393-1
Space charge effects play important roles in ion trap operations, which typically limit the ion trapping capacity, dynamic range, mass accuracy, and resolving power of a quadrupole ion trap. In this study, a rhombic ion excitation and ejection method was proposed to minimize space charge effects in a linear ion trap. Instead of applying a single dipolar AC excitation signal, two dipolar AC excitation signals with the same frequency and amplitude but 90° phase difference were applied in the x- and y-directions of the linear ion trap, respectively. As a result, mass selective excited ions would circle around the ion cloud located at the center of the ion trap, rather than go through the ion cloud. In this work, excited ions were then axially ejected and detected, but this rhombic ion excitation method could also be applied to linear ion traps with ion radial ejection capabilities. Experiments show that space charge induced mass resolution degradation and mass shift could be alleviated with this method. For the experimental conditions in this work, space charge induced mass shift could be decreased by ~50%, and the mass resolving power could be improved by ~2 times at the same time.
Co-reporter:Hui Qu, Fanchen Kong, Guanjun Wang, and Mingfei Zhou
The Journal of Physical Chemistry A 2016 Volume 120(Issue 37) pp:7287-7293
Publication Date(Web):August 29, 2016
DOI:10.1021/acs.jpca.6b08310
Heteronuclear transition metal carbonyl cluster cations FeM(CO)8+ (M = Co, Ni and Cu) and MCu(CO)7+ (M = Co and Ni) are produced via a laser vaporization supersonic cluster ion source in the gas phase, which are each mass-selected and studied by infrared photodissociation spectroscopy in the carbonyl stretching frequency region. Their geometric and electronic structures are established by comparison of the experimental spectra with those derived from density functional theoretical calculations. The FeM(CO)8+ (M = Co, Ni, Cu) complexes are determined to have eclipsed (CO)5Fe–M(CO)3+ structures, and the MCu(CO)7+ (M = Co, Ni) ions are characterized to have staggered (CO)4M–Cu(CO)3+ structures. Natural bonding orbital analysis indicates that the positive charge is mainly distributed on the M(CO)3 fragment. The metal–metal interaction involves an σ-type (OC)4,5M→M(CO)3+ dative bonding.
Co-reporter:Qingnan Zhang, Hui Qu, Mohua Chen, and Mingfei Zhou
The Journal of Physical Chemistry A 2016 Volume 120(Issue 3) pp:425-432
Publication Date(Web):January 6, 2016
DOI:10.1021/acs.jpca.5b11809
The reactions of carbon dioxide with scandium monoxide molecules and scandium atoms are investigated using matrix isolation infrared spectroscopy in solid neon. The species formed are identified by the effects of isotopic substitution on their infrared spectra as well as density functional calculations. The results show that the ground state ScO molecule reacts with carbon dioxide to form the carbonate complex ScCO3 spontaneously on annealing. The ground state Sc atom reacts with two carbon dioxide molecules to give the carbonate carbonyl complex OCScCO3 via the previously reported OScCO insertion intermediate on annealing. The observation of these spontaneous reactions is consistent with theoretical predictions that both the Sc + 2CO2 → OCScCO3 and ScO + CO2 → ScCO3 reactions are thermodynamically exothermic and are kinetically facile, requiring little or no activation energy.
Co-reporter:Jiwen Jian;Jiaye Jin;Hui Qu;Dr. Hailu Lin;Dr. Mohua Chen;Dr. Guanjun Wang; Mingfei Zhou;Dr. Diego M. Andrada;Dr. Markus Hermann; Gernot Frenking
Chemistry - A European Journal 2016 Volume 22( Issue 7) pp:2376-2385
Publication Date(Web):
DOI:10.1002/chem.201504475
Abstract
A combined experimental and theoretical study on the main-group tricarbonyls [B(CO)3] in solid noble-gas matrices and [C(CO)3]+ in the gas phase is presented. The molecules are identified by comparing the experimental and theoretical IR spectra and the vibrational shifts of nuclear isotopes. Quantum chemical ab initio studies suggest that the two isoelectronic species possess a tilted η1(μ1-CO)-bonded carbonyl ligand, which serves as an unprecedented one-electron donor ligand. Thus, the central atoms in both complexes still retain an 8-electron configuration. A thorough analysis of the bonding situation gives quantitative information about the donor and acceptor properties of the different carbonyl ligands. The linearly bonded CO ligands are classical two-electron donors that display classical σ-donation and π-back-donation following the Dewar–Chatt–Duncanson model. The tilted CO ligand is a formal one-electron donor that is bonded by σ-donation and π-back-donation that involves the singly occupied orbital of the radical fragments [B(CO)2] and [C(CO)2]+.
Co-reporter:Yuzhen Li, Yu Gong, Xiaojie Zhou, Jing Su, Jun Li, Mingfei Zhou
Journal of Molecular Spectroscopy 2015 310() pp: 50-56
Publication Date(Web):
DOI:10.1016/j.jms.2014.12.013
Co-reporter:Ning Zhang, Mingbiao Luo, Chaoxian Chi, Guanjun Wang, Jieming Cui, and Mingfei Zhou
The Journal of Physical Chemistry A 2015 Volume 119(Issue 18) pp:4142-4150
Publication Date(Web):April 14, 2015
DOI:10.1021/acs.jpca.5b02442
Mass-selected heteronuclear iron–copper carbonyl cluster anions CuFe(CO)n– (n = 4–7) are studied by infrared photodissociation spectroscopy in the carbonyl stretching frequency region in the gas phase. The cluster anions are produced via a laser vaporization supersonic cluster ion source. Their geometric structures are determined by comparison of the experimental spectra with those calculated by density functional theory. The experimentally observed CuFe(CO)n– (n = 4–7) cluster anions are characterized to have (OC)4Fe–Cu(CO)n−4 structures, each involving a C3v symmetry Fe(CO)4– building block. Bonding analysis indicates that the Fe–Cu bond in the CuFe(CO)n– (n = 4–7) cluster anions is a σ type single bond with the iron center possessing the most favored 18-electron configuration. The results provide important new insight into the structure and bonding of hetronuclear transition metal carbonyl cluster anions.
Co-reporter: Mohua Chen;Qingnan Zhang; Mingfei Zhou;Dr. Diego M. Andrada; Gernot Frenking
Angewandte Chemie International Edition 2015 Volume 54( Issue 1) pp:124-128
Publication Date(Web):
DOI:10.1002/anie.201406264
Abstract
The complexes OCBeCO3 and COBeCO3 have been isolated in a low-temperature neon matrix. The more stable isomer OCBeCO3 has a very high CO stretching mode of 2263 cm−1, which is blue-shifted by 122 cm−1 with respect to free CO and 79 cm−1 higher than in OCBeO. Bonding analysis of the complexes shows that OCBeO has a stronger OCBeY bond than OCBeCO3 because it encounters stronger π backdonation. The isomers COBeCO3 and COBeO exhibit red-shifted CO stretching modes with respect to free CO. The inverse change of CO stretching frequency in OCBeY and COBeY is explained with the reversed polarization of the σ and π bonds in CO.
Co-reporter: Mohua Chen;Qingnan Zhang; Mingfei Zhou;Dr. Diego M. Andrada; Gernot Frenking
Angewandte Chemie 2015 Volume 127( Issue 1) pp:126-130
Publication Date(Web):
DOI:10.1002/ange.201406264
Abstract
The complexes OCBeCO3 and COBeCO3 have been isolated in a low-temperature neon matrix. The more stable isomer OCBeCO3 has a very high CO stretching mode of 2263 cm−1, which is blue-shifted by 122 cm−1 with respect to free CO and 79 cm−1 higher than in OCBeO. Bonding analysis of the complexes shows that OCBeO has a stronger OCBeY bond than OCBeCO3 because it encounters stronger π backdonation. The isomers COBeCO3 and COBeO exhibit red-shifted CO stretching modes with respect to free CO. The inverse change of CO stretching frequency in OCBeY and COBeY is explained with the reversed polarization of the σ and π bonds in CO.
Co-reporter:Qingnan Zhang;Wan-Lu Li;Cong-Qiao Xu;Dr. Mohua Chen; Mingfei Zhou; Jun Li;Dr. Diego M. Andrada; Gernot Frenking
Angewandte Chemie 2015 Volume 127( Issue 38) pp:11230-11235
Publication Date(Web):
DOI:10.1002/ange.201503686
Abstract
We report the synthesis and spectroscopic characterization of the boron dicarbonyl complex [B(CO)2]−. The bonding situation is analyzed and compared with the aluminum homologue [Al(CO)2]− using state-of-the-art quantum chemical methods.
Co-reporter:Qingnan Zhang, Mohua Chen, Mingfei Zhou, Diego M. Andrada, and Gernot Frenking
The Journal of Physical Chemistry A 2015 Volume 119(Issue 11) pp:2543-2552
Publication Date(Web):October 16, 2014
DOI:10.1021/jp509006u
The novel neon complex NeBeCO3 has been prepared in a low-temperature neon matrix via codeposition of laser-evaporated beryllium atoms with O2 + CO/Ne. Doping by the heavier noble gas atoms argon, krypton and xenon yielded the associated adducts NgBeCO3 (Ng = Ar, Kr, Xe). The noble gas complexes have been identified via infrared spectroscopy. Quantum chemical calculations of NgBeCO3 and NgBeO (Ng = He, Ne, Ar, Kr, Xe) using ab initio methods and density functional theory show that the Ng–BeCO3 bonds are slightly longer and weaker than the Ng–BeO bonds. The energy decomposition analysis of the Ng–Be bonds suggests that the attractive interactions come mainly from the Ng → BeCO3 and Ng → BeO σ donation.
Co-reporter:Qingnan Zhang;Wan-Lu Li;Cong-Qiao Xu;Dr. Mohua Chen; Mingfei Zhou; Jun Li;Dr. Diego M. Andrada; Gernot Frenking
Angewandte Chemie International Edition 2015 Volume 54( Issue 38) pp:11078-11083
Publication Date(Web):
DOI:10.1002/anie.201503686
Abstract
We report the synthesis and spectroscopic characterization of the boron dicarbonyl complex [B(CO)2]−. The bonding situation is analyzed and compared with the aluminum homologue [Al(CO)2]− using state-of-the-art quantum chemical methods.
Co-reporter:Yuzhen Li, Lichen Wang, Hui Qu, Guanjun Wang, and Mingfei Zhou
The Journal of Physical Chemistry A 2015 Volume 119(Issue 15) pp:3577-3586
Publication Date(Web):March 26, 2015
DOI:10.1021/acs.jpca.5b00747
The [M(NO)n]+ cation complexes (M = Au and Ag) are studied for exploring the coordination and bonding between nitric oxide and noble metal cations. These species are produced in a laser vaporization supersonic ion source and probed by infrared photodissociation spectroscopy in the NO stretching frequency region using a collinear tandem time-of-flight mass spectrometer. The geometric and electronic structures of these complexes are determined by comparison of the distinctive experimental spectra with simulated spectra derived from density functional theory calculations. All of these noble metal nitrosyl cation complexes are characterized to have bent NO ligands serving as one-electron donors. The spectrum of [Au(NO)2Ar]+ is consistent with 2-fold coordination with a near linear N–Au–N arrangement for this ion. The [Au(NO)n]+ (n = 3–4) cations are determined to be a mixture of 2-fold coordinated form and 3- or 4-fold coordinated form. In contrast, the spectra of [Ag(NO)n]+ (n = 3–6) provide evidence for the completion of the first coordination shell at n = 5. The high [Au(NO)n]+ and [Ag(NO)n]+ (n ≥ 3 for Au, n ≥ 4 for Ag) complexes each involve one or more (NO)2 dimer ligands, as observed in the copper nitrosyl cation complexes, indicating that ligand–ligand coupling plays an important role in the structure and bonding of noble metal nitrosyl cation complexes.
Co-reporter:Caixia Wang, Jiwen Jian, Zhen Hua Li, Mohua Chen, Guanjun Wang, and Mingfei Zhou
The Journal of Physical Chemistry A 2015 Volume 119(Issue 35) pp:9286-9293
Publication Date(Web):August 18, 2015
DOI:10.1021/acs.jpca.5b07089
The infrared spectra of mass-selected Ni(O2)n+ (n = 2–4) and their argon-tagged complexes are measured by infrared photodissociation spectroscopy in the gas phase. The experimental spectra provide distinctive patterns allowing the determination of their geometric and electronic structures by comparison with the simulated vibrational spectra from density functional theory calculations. The [Ni(O2)2Ar2]+ cation complex was determined to have D2h symmetry involving a Ni(O2)2+ core ion with two equivalent superoxide ligands side-on bound to a Ni3+ cation center. The higher Ni(O2)3+ and Ni(O2)4+ cation complexes were determined to have structures with a chemically bound Ni(O2)2+ core ion that is weakly coordinated by neutral O2 molecule(s).
Co-reporter:Lichen Wang, Guanjun Wang, Hui Qu, Zhen Hua Li and Mingfei Zhou
Physical Chemistry Chemical Physics 2014 vol. 16(Issue 22) pp:10788-10798
Publication Date(Web):06 Mar 2014
DOI:10.1039/C4CP00557K
The infrared spectra of mass-selected mononuclear copper nitrosyl cation complexes [Cu(NO)n]+ with n = 1–5 and their argon tagged complexes are measured via infrared photodissociation spectroscopy in the nitrosyl stretching frequency region in the gas phase. The experimental spectra provide distinctive patterns allowing the determination of the geometries and electronic structures of these complexes by comparison with the predicted spectra from density functional theory computations. The argon tagged [Cu(NO)2Ar2]+ and [Cu(NO)3Ar]+ complexes as well as the higher n = 4 and 5 complexes each involve a bidentate (NO)2 dimer ligand, suggesting that ligand–ligand coupling plays an important role in the bonding of these cation systems. The results also show that argon tagging has a strong influence on the geometric and electronic structures of the n = 2 and 3 complexes. The [Cu(NO)4]+ cation is the most intense peak in the mass spectrum, which is characterized to be the fully coordinated ion with a D2d structure involving two (NO)2 units but with only 14-valence electrons on Cu. The [Cu(NO)5]+ cation complex is determined to involve a [Cu(NO)4]+ core ion that is coordinated by an external NO ligand.
Co-reporter:Caixia Wang, Jiwen Jian, Guanjun Wang, Zhen Hua Li, and Mingfei Zhou
The Journal of Physical Chemistry A 2014 Volume 118(Issue 25) pp:4519-4526
Publication Date(Web):June 4, 2014
DOI:10.1021/jp504107k
Infrared spectra of mass-selected oxygen-rich iron dioxygen complexes Fe(O2)n+ with n = 3–5 are measured via infrared photodissociation spectroscopy in the gas phase. These cation complexes are produced via a laser vaporization supersonic ion source. The structures are established by comparison of the experimental spectra with the simulated spectra derived from density functional calculations. All of the Fe(O2)n+ complexes studied have a single IR-active band in the 1050–1100 cm–1 region, arising from the O–O stretching vibration of the superoxo ligand(s). These complexes are determined to have structures with a chemically bound Fe(O2)2+ core ion that is weakly coordinated by neutral O2 molecules. The Fe(O2)2+ core ion has a planar D2h symmetry with two equivalent side-on superoxo ligands bound to an Fe3+ cation center.
Co-reporter:Jieming Cui, Xiaojie Zhou, Guanjun Wang, Chaoxian Chi, Zhen Hua Li, and Mingfei Zhou
The Journal of Physical Chemistry A 2014 Volume 118(Issue 15) pp:2719-2727
Publication Date(Web):March 27, 2014
DOI:10.1021/jp411237p
Infrared spectra of mass-selected homoleptic cobalt carbonyl cluster cations including dinuclear Co2(CO)8+ and Co2(CO)9+, trinuclear Co3(CO)10+ and Co3(CO)11+, as well as tetranuclear Co4(CO)12+ are measured via infrared photodissociation spectroscopy in the carbonyl stretching frequency region. The geometric structures of these complexes are determined by comparison of the experimental spectra with those calculated by density functional theory. The Co2(CO)8+ cation is characterized to have a Co–Co bonded structure with Cs symmetry involving a bridging CO ligand. The Co2(CO)9+ cation is determined to be a mixture of the CO-tagged Co2(CO)8+–CO complex and the Co(CO)5+–Co(CO)4 ion–molecular complex. The Co3(CO)10+ cation is the coordination-saturated trinuclear cluster, which is characterized to have a triangle Co3 core with C2 symmetry involving two edge-bridging and eight terminal CO ligands. The Co3(CO)11+ cation is a weakly bound complex involving a Co3(CO)10+ core ion. The Co4(CO)12+ cluster cation is deduced to have a tetrahedral Co4+ core structure with three edge-bridging and nine terminal carbonyls.
Co-reporter:Qingnan Zhang, Mohua Chen, and Mingfei Zhou
The Journal of Physical Chemistry A 2014 Volume 118(Issue 31) pp:6009-6017
Publication Date(Web):July 17, 2014
DOI:10.1021/jp505740j
The reactions from codeposition of laser-ablated chromium atoms with carbon dioxide in excess neon are studied by infrared absorption spectroscopy. The species formed are identified by the effects of isotopic substitution on their infrared spectra. Density functional calculations are performed to support the spectral assignments and to interpret the geometric and electronic structures of the experimentally observed species. Besides the previously reported insertion products OCrCO and O2Cr(CO)2, the one-to-one Cr(CO2) complex and the one-to-two Cr(CO2)2 complex as well as the CrOCrCO and OCCrCO3 complexes are also formed. The Cr(CO2) complex is characterized to be side-on η2-C,O-coordinated. The Cr(CO2)2 complex is identified to involve a side-on η2-C,O-coordinated CO2 and an end-on η1-O-coordinated CO2. OCCrCO3 is a carbonate carbonyl complex predicted to have a planar structure with a η2-O,O-coordinated carbonate ligand. The CrOCrCO complex is predicted to be linear with a high-spin ground state. Besides the neutral molecules, charged species are also produced. The Cr(CO2)+ and Cr(CO2)2+ cation complexes are characterized to have linear end-on η1-O-coordinated structures with blue-shifted antisymmetric CO2 stretching vibrational frequencies. The OCrCO– anion is bent with the Cr–O and CO stretching frequencies red-shifted from those of OCrCO neutral molecule.
Co-reporter:Lichen Wang, Guanjun Wang, Hui Qu, Caixia Wang, and Mingfei Zhou
The Journal of Physical Chemistry A 2014 Volume 118(Issue 10) pp:1841-1849
Publication Date(Web):February 21, 2014
DOI:10.1021/jp500152c
Infrared spectra of mass-selected mononuclear iron nitrosyl cations Fe(NO)n+ with n = 1–5 and their argon tagged complexes are measured via infrared photodissociation spectroscopy in the nitrosyl stretching frequency region in the gas phase. The structures are established by comparison of the experimental spectra with the simulated spectra derived from density functional calculations. Two IR active bands were observed for the argon-tagged Fe(NO)2+ and Fe(NO)3+ complexes, consistent with theoretical predictions that these complexes have bent C2v and nonplanar C3v symmetry, respectively. The Fe(NO)4+ complex was characterized to have a completed coordination sphere with 17 electrons containing a bent one-electron NO ligand and three three-electron NO ligands. The Fe(NO)5+ complex was determined to involve a Fe(NO)4+ core ion that is solvated by an external NO molecule.
Co-reporter:Jieming Cui, Guanjun Wang, Xiaojie Zhou, Chaoxian Chi, Zhen Hua Li, Zhipan Liu and Mingfei Zhou
Physical Chemistry Chemical Physics 2013 vol. 15(Issue 25) pp:10224-10232
Publication Date(Web):04 Feb 2013
DOI:10.1039/C3CP44588G
Infrared spectra of mass-selected homoleptic nickel carbonyl cluster cations including dinuclear Ni2(CO)7+ and Ni2(CO)8+, trinuclear Ni3(CO)9+ and tetranuclear Ni4(CO)11+ are measured via infrared photodissociation spectroscopy in the carbonyl stretching frequency region. The structures are established by comparison of the experimental spectra with simulated spectra derived from density functional calculations. The Ni2(CO)7+ cation is characterized to have an unbridged asymmetric (OC)4Ni–Ni(CO)3+ structure with a Ni–Ni single bond. The Ni2(CO)8+ cation has a Ni–Ni half-bonded D3d structure with both nickel centers exhibiting an 18-electron configuration. The trinuclear Ni3(CO)9+ cluster cation is determined to have an open chain like (OC)4Ni–NiCO–Ni(CO)4 structure. The tetranuclear Ni4(CO)11+ cluster cation is determined to have a tetrahedral structure with two-center and three-center bridge-bonded carbonyl units. These nickel carbonyl cluster cations all involve trigonal pyramid like Ni(CO)4 building blocks that satisfy the 18-electron configuration of the nickel centers.
Co-reporter:Mohua Chen, Mingfei Zhou
Chemical Physics Letters 2013 Volume 578() pp:28-32
Publication Date(Web):18 July 2013
DOI:10.1016/j.cplett.2013.05.044
•The chloromethylene hydroperoxide cation, HC(Cl)OOH+ is produced in solid argon matrix.•The infrared spectrum of HC(Cl)OOH+ is reported and assigned on the basis of isotopic substitutions.•HC(Cl)OOH+ is predicted to have a singlet ground state with planar Cs symmetry.Infrared spectrum of the chloromethylene hydroperoxide cation, HC(Cl)OOH+ in solid argon is reported. The cation is produced by co-condensation of dichloromethane and dioxygen mixtures with high-frequency discharged argon at 4 K followed by visible light excitation. On the basis of isotopic substitutions as well as quantum chemical frequency calculations, absorptions at 3452.7, 3052.0, 1499.6, 976.9, 855.4 and 956.1 cm−1 are assigned to the O–H, C–H, CO, C–Cl and O–O stretching and out-of-plane CH wagging vibrations of the chloromethylene hydroperoxy cation. The cation was predicted to have a singlet ground state with planar Cs symmetry.
Co-reporter:Xiaojie Zhou, Mohua Chen, and Mingfei Zhou
The Journal of Physical Chemistry A 2013 Volume 117(Issue 26) pp:5463-5471
Publication Date(Web):May 29, 2013
DOI:10.1021/jp4034134
Reactions of vanadium dioxide molecules with acetylene have been studied by matrix isolation infrared spectroscopy. Reaction intermediates and products are identified on the basis of isotopic substitutions as well as density functional frequency calculations. Ground state vanadium dioxide molecule reacts with acetylene in forming the side-on-bonded VO2(η2-C2H2) and VO2(η2-C2H2)2 complexes spontaneously on annealing in solid neon. The VO2(η2-C2H2) complex is characterized to have a 2B2 ground state with C2v symmetry, whereas the VO2(η2-C2H2)2 complex has a 2A ground state with C2 symmetry. The VO2(η2-C2H2) and VO2(η2-C2H2)2 complexes are photosensitive. The VO2(η2-C2H2) complex rearranges to the OV(OH)CCH molecule upon UV–vis light excitation.
Co-reporter:Xiaojie Zhou, Jieming Cui, Zhen Hua Li, Guanjun Wang, Zhipan Liu, and Mingfei Zhou
The Journal of Physical Chemistry A 2013 Volume 117(Issue 7) pp:1514-1521
Publication Date(Web):January 18, 2013
DOI:10.1021/jp3120429
Mononuclear and dinuclear titanium carbonyl cation complexes including Ti(CO)6+, Ti(CO)7+, TiO(CO)5+, Ti2(CO)9+ and Ti2O(CO)9+ are produced via a laser vaporization supersonic cluster source. The ions are mass selected in a tandem time-of-flight mass spectrometer and studied with infrared photodissociation spectroscopy in the CO stretching frequency region. The structures are established by comparison of the experimental spectra with simulated spectra derived from density functional calculations. Only one IR band is observed for the 15-electron Ti(CO)6+ cation, which is characterized to have an octahedral Oh structure. The Ti(CO)7+ cation is determined to be a weakly bound complex involving a Ti(CO)6+ core ion instead of the seventh coordinated ion. The TiO(CO)5+ cation has a completed coordination sphere with a C4v structure. The Ti2(CO)9+ cation is determined to have a doublet Cs structure with two four-electron donor side-on bridging CO groups and one semibridging CO group. The Ti2O(CO)9+ cation has a doublet Cs structure involving a planar cyclic Ti2O(η2-μ-CO) core with a four electron donor side-on bridging CO. Bonding analysis indicates that the Ti2(CO)9+ and Ti2O(CO)9+ cations each have a Ti–Ti single bond. The results suggest that metal–metal multiple bonding is not favorable, and the oxophilic titanium centers failed to satisfy the 18-electron configuration in these metal carbonyl complexes.
Co-reporter:Jieming Cui, Xiaojie Zhou, Guanjun Wang, Chaoxian Chi, Zhipan Liu, and Mingfei Zhou
The Journal of Physical Chemistry A 2013 Volume 117(Issue 33) pp:7810-7817
Publication Date(Web):July 29, 2013
DOI:10.1021/jp405250y
Infrared spectra of mass-selected homoleptic copper carbonyl cluster cations including dinuclear Cu2(CO)6+ and Cu2(CO)7+, trinuclear Cu3(CO)7+, Cu3(CO)8+, and Cu3(CO)9+, and tetranuclear Cu4(CO)8+ are measured via infrared photodissociation spectroscopy in the carbonyl stretching frequency region. The structures are established by comparison of the experimental spectra with simulated spectra derived from density functional calculations. The Cu2(CO)6+ cation is characterized to have an unbridged D3d structure with a Cu–Cu half bond. The Cu2(CO)7+ cation is determined to be a weakly bound complex involving a Cu2(CO)6+ core ion. The trinuclear Cu3(CO)7+ and Cu3(CO)8+ cluster cations are determined to have triangle Cu3 core structures with C2 symmetry involving two Cu(CO)3 groups and one Cu(CO)x group (x = 1 or 2). In contrast, the trinuclear Cu3(CO)9+ cluster cation is determined to have an open chain-like (OC)3Cu–Cu(CO)3–Cu(CO)3 structure. The tetranuclear Cu4(CO)8+ cluster cation is characterized to have a tetrahedral Cu4+ core structure with all carbonyl groups terminally bonded.
Co-reporter:Caixia Wang, Mohua Chen, Zhen Hua Li, and Mingfei Zhou
The Journal of Physical Chemistry A 2013 Volume 117(Issue 44) pp:11217-11224
Publication Date(Web):October 11, 2013
DOI:10.1021/jp406126c
The reactions of bismuth atoms and O2 have been investigated using matrix isolation infrared spectroscopy and density functional theory calculations. The ground state bismuth atoms react with dioxygen to form the BiOO and Bi(O2)2 complexes spontaneously on annealing. The BiOO molecule is characterized to be an end-on bonded superoxide complex, while the Bi(O2)2 molecule is characterized to be a superoxo bismuth peroxide complex, [Bi3+(O2–)(O22-)]. Under UV–visible light irradiation, the Bi(O2)2 complex rearranges to the more stable OBiOOO isomer, an end-on bonded bismuth monoxide-ozonide complex. The end-on-bonded OBiOOO complex further rearranges to a more stable side-on bonded OBiO3 isomer upon sample annealing. In addition, the bent bismuth dioxide anion is also formed and assigned.
Co-reporter:Wenhua Xu, Xi Jin, Mohua Chen, Pekka Pyykkö, Mingfei Zhou and Jun Li
Chemical Science 2012 vol. 3(Issue 5) pp:1548-1554
Publication Date(Web):22 Feb 2012
DOI:10.1039/C2SC00998F
The reactions of Group-3 metal atoms with carbon monoxide in solid argon have been studied using matrix isolation infrared absorption spectroscopy. The lanthanide monocarbonyls LnCO were produced spontaneously on annealing. The observations on LnCO, Ln = Pr, Nd, Sm, Eu, Tb, Dy, Ho, and Er are new. We also theoretically study the structure, bonding, and C–O stretch infrared frequencies. The covalent M–C bonding contains both M ← C σ donation from the carbon lone pair, and M 5d → CO 2π* back donation contributions. In addition to the open 4fn shells, the total spin, as found earlier, may have contributions from an M ‘σ doughnut’ and the M–C π bond, in a σ1π1, σ1π2 high-spin, or σ2π1 low-spin configuration. They form at least a single-bond, and those with the σ1π2 configuration approach a double bond in length. The weakening of the C–O bonding is related to the back donation to the antibonding C–O 2π* orbital.
Co-reporter:Chaoxian Chi, Jieming Cui, Zhen Hua Li, Xiaopeng Xing, Guanjun Wang and Mingfei Zhou
Chemical Science 2012 vol. 3(Issue 5) pp:1698-1706
Publication Date(Web):29 Feb 2012
DOI:10.1039/C2SC20119D
Infrared spectra of mass-selected homoleptic dinuclear iron carbonyl cluster anions Fe2(CO)n− (n = 4–9) are measured via infrared photodissociation spectroscopy in the carbonyl stretching frequency region. The cluster anions are produced via a laser vaporization supersonic cluster source. Density functional calculations have been performed and the calculated vibrational spectra are compared to the experimental data to identify the gas-phase structures of the cluster anions. The experimentally observed Fe2(CO)n− (n = 4–7) cluster anions are characterized to have unusual asymmetric (OC)4Fe–Fe(CO)n−4 structures, which also correspond to the computed lowest energy structures. The experimentally observed Fe2(CO)8− cluster anion is determined to have an unbridged structure instead of the previously reported dibridged structure. The Fe2(CO)9− cluster anion is determined to involve a Fe2(CO)8− core anion that is solvated by an external CO molecule. Bonding analysis indicates that these anions each have a Fe–Fe single bond to satisfy the 18-electron configuration of one iron center. The results provide important new insight into the structure and bonding mechanisms of transition-metal carbonyl clusters.
Co-reporter:Guanjun Wang, Jieming Cui, Chaoxian Chi, Xiaojie Zhou, Zhen Hua Li, Xiaopeng Xing and Mingfei Zhou
Chemical Science 2012 vol. 3(Issue 11) pp:3272-3279
Publication Date(Web):15 Aug 2012
DOI:10.1039/C2SC20947K
Infrared spectra of mass-selected homoleptic iron carbonyl cluster cations including mononuclear Fe(CO)5+ and Fe(CO)6+, dinuclear Fe2(CO)8+ and Fe2(CO)9+, and trinuclear Fe3(CO)12+ are measured via infrared photodissociation spectroscopy in the carbonyl stretching frequency region. The structures are established by comparison of the experimental spectra with simulated spectra derived from density functional calculations. Only one IR band is observed for the Fe(CO)5+ cation, which is predicted to have a C4v structure. The Fe(CO)6+ cation is determined to be a weakly bound complex involving a Fe(CO)5+ core ion. In contrast to neutral clusters which have symmetric structures with two and three bridging carbonyl ligands, the dinuclear Fe2(CO)8+ and Fe2(CO)9+ cations are characterized to have unbridged asymmetric (OC)5Fe–Fe(CO)n+ (n = 3 and 4) structures. The trinuclear Fe3(CO)12+ cluster cation is determined to have an open chain like (OC)5Fe–Fe(CO)2–Fe(CO)5 structure instead of the triangular structure with two bridging CO groups for the Fe3(CO)12 neutral. The di- and trinuclear cluster cations all involve a square pyramid like Fe(CO)5 building block that satisfies the 18-electron configuration of this iron center. The Fe(CO)5 building block is isolobal to the CH3 fragment in hydrocarbon chemistry, the Fe2(CO)9+ and Fe3(CO)12+ cluster cations may be considered through isolobality to be metal carbonyl analogues of the ethyl and isopropyl cations.
Co-reporter:Chaoyang Zhang, Mohua Chen, Guanjun Wang, Xiaolin Wang, Mingfei Zhou
Chemical Physics 2012 Volume 392(Issue 1) pp:198-204
Publication Date(Web):2 January 2012
DOI:10.1016/j.chemphys.2011.11.015
Abstract
The photo-induced isomerization reactions of ortho-, meta- and para-nitrotoluene molecules were investigated by matrix isolation infrared spectroscopy and quantum chemical calculations. Under UV irradiation of ortho-nitrotoluene in solid argon, the hydrogen atom transfer isomer was formed, as reported previously. It was found that the hydrogen atom transfer isomer is unstable and rearranged to its nitro isomer upon annealing. In addition, the nitrite isomer as well as its dissociation product tolyloxy radical was also formed. Only the nitrite isomers and the tolyloxy radicals were formed upon UV excitation of the meta- and para-nitrotoluene molecules. Infrared spectra and vibrational frequency assignments of the newly observed nitrite isomers and tolyloxy radicals are reported, which are supported by quantum chemical calculations.
Co-reporter:Jieming Cui;Xiaopeng Xing;Chaoxian Chi;Guanjun Wang;Zhipan Liu
Chinese Journal of Chemistry 2012 Volume 30( Issue 9) pp:2131-2137
Publication Date(Web):
DOI:10.1002/cjoc.201200595
Abstract
Infrared spectra of mass-selected homoleptic dinuclear palladium carbonyl cluster cations Pd2(CO)n+ (n=5–8) are measured via infrared photodissociation spectroscopy in the carbonyl stretching frequency region. The structures are established by comparison of the experimental spectra with simulated spectra derived from density functional calculations. The Pd2(CO)5+ cation is characterized to have two weakly semibridging CO groups with C2 symmetry. The Pd2(CO)6+ and Pd2(CO)7+ cations are determined to involve one weakly semibridging CO group. The Pd2(CO)8+ cation is a CO coordination saturated cluster, which is determined to have a D2d structure with all of the carbonyl groups terminally bonded. Bonding analysis indicates that these cluster cations each has a PdPd half bond. The PdPd distance increases with the number of CO ligands.
Co-reporter:Guanjun Wang, Chaoxian Chi, Jieming Cui, Xiaopeng Xing, and Mingfei Zhou
The Journal of Physical Chemistry A 2012 Volume 116(Issue 10) pp:2484-2489
Publication Date(Web):February 23, 2012
DOI:10.1021/jp211936b
The infrared photodissociation spectroscopy of mass-selected mononuclear iron carbonyl anions Fe(CO)n– (n = 2–8) were studied in the carbonyl stretching frequency region. The FeCO– anion does not fragment when excited with infrared light. Only a single IR active band was observed for the Fe(CO)2– and Fe(CO)3– anions, consistent with theoretical predictions that these complexes have linear D∞h and planar D3h symmetry, respectively. The Fe(CO)4– anion is the most intense peak in the mass spectra and was characterized to have a completed coordination sphere with high stability. Anion clusters larger than n = 4 were determined to involve a Fe(CO)4– core anion that is progressively solvated by external CO molecules. Three CO stretching vibrational fundamentals were observed for the Fe(CO)4– core anion, indicating that the Fe(CO)4– anion has a C3v structure. All the carbonyl stretching frequencies of the Fe(CO)n– anion complexes are red-shifted with respect to those of the corresponding neutrals.
Co-reporter:Yuzhen Li, Guanjun Wang, Caixia Wang, and Mingfei Zhou
The Journal of Physical Chemistry A 2012 Volume 116(Issue 44) pp:10793-10801
Publication Date(Web):October 22, 2012
DOI:10.1021/jp3094963
Gold cation–water complexes with attached argon atoms are produced via a laser vaporization supersonic cluster source. The [Au(H2O)nArx]+ (n = 1–8; x = 1 or 2) complexes are each mass selected and studied by infrared photodissociation spectroscopy in the OH stretching frequency region to explore the coordination and solvation structures of the Au+ cation. Density functional calculations have been performed, and the calculated vibrational spectra are compared to the experimental spectra to identify the gas-phase structures of the Au(H2O)n+ complexes. Confirming previous theoretical predications, the first coordination shell of the Au+ cation contains two water molecules forming a linear O–Au+–O arrangement; subsequent water molecules bind to the two H2O ligands of the Au(H2O)2+ core ion via hydrogen bond forming of the second hydration shell, which is complete at n = 6. For the complexes with n ≤ 7, the experimental spectrum can in general be assigned to the predicted global minimum structure. However, the spectrum suggests that two or more conformers coexist for the n = 8 complex, indicating that the identification of a single global minimum becomes less important upon increasing the number of solvating water molecules.
Co-reporter:Xiaojie Zhou, Jieming Cui, Zhen Hua Li, Guanjun Wang, and Mingfei Zhou
The Journal of Physical Chemistry A 2012 Volume 116(Issue 50) pp:12349-12356
Publication Date(Web):December 3, 2012
DOI:10.1021/jp3108123
Infrared spectra of mass-selected homoleptic dinuclear chromium carbonyl cluster cations Cr2(CO)n+ with n = 7–9 are measured via infrared photodissociation spectroscopy in the carbonyl stretching frequency region in the gas phase. The structures are established by comparison of the experimental spectra with the simulated spectra derived from density functional calculations. The Cr2(CO)n+ cluster cations are characterized to have the (OC)5Cr–C–O–Cr(CO)n−6+ structures with a linear bridging carbonyl group bonded to one chromium atom through its carbon atom and to the other chromium atom through its oxygen atom. The cluster cations all have a sextet ground state with the positive charge and the unpaired electrons located on the Cr(CO)n−6 moiety. The formation of the linear bridging structures without Cr–Cr bonding can be rationalized that chromium forms strong Cr–CO bonds but weak Cr–Cr bonds.
Co-reporter:Jia Zhuang, Zhen Hua Li, Kangnian Fan, and Mingfei Zhou
The Journal of Physical Chemistry A 2012 Volume 116(Issue 13) pp:3388-3395
Publication Date(Web):March 15, 2012
DOI:10.1021/jp301025n
The reactions of titanium monoxide and dioxide molecules with carbon dioxide were investigated by matrix isolation infrared spectroscopy. It was found that the titanium monoxide molecule is able to activate carbon dioxide to form the titanium dioxide–carbon monoxide complex upon visible light excitation via a weakly bound TiO(η1-OCO) intermediate in solid neon. In contrast, the titanium dioxide molecule reacted with carbon dioxide to form the titanium monoxide–carbonate complex spontaneously on annealing. Theoretical calculations predicted that both activation processes are thermodynamically exothermic and kinetically facile.
Co-reporter:Mingfei Zhou, Zijian Zhou, Jia Zhuang, Zhen Hua Li, Kangnian Fan, Yanying Zhao, and Xuming Zheng
The Journal of Physical Chemistry A 2011 Volume 115(Issue 50) pp:14361-14369
Publication Date(Web):November 7, 2011
DOI:10.1021/jp208291g
Carbon dioxide coordination and activation by niobium oxide molecules were studied by matrix isolation infrared spectroscopy. It was found that the niobium monoxide molecule reacted with carbon dioxide to form the niobium dioxide carbonyl complex NbO2(η1-CO) spontaneously on annealing in solid neon. The observation of the spontaneous reaction is consistent with theoretical predictions that this carbon dioxide activation process is both thermodynamically exothermic and kinetically facile. In contrast, four niobium dioxide–carbon dioxide complexes exhibiting three different coordination modes of CO2 were formed from the reactions between niobium dioxide and carbon dioxide, which proceeded with the initial formation of the η1-O bound NbO2(η1-OCO) and NbO2(η1-OCO)2 complexes on annealing. The NbO2(η1-OCO) complex rearranged to the η2-O,O bound NbO2(η2-O2C) isomer under visible light irradiation, while the NbO2(η1-OCO)2 complex isomerized to the NbO2(η1-OCO)(η2-OC)O structure involving an η2-C,O ligand under IR excitation. In these niobium dioxide carbon dioxide complexes, the η1-O coordinated CO2 ligand serves as an electron donor, whereas both the η2-C,O and η2-O,O coordinated CO2 ligands act as electron acceptors.
Co-reporter:Mingfei Zhou, Jia Zhuang, Zijian Zhou, Zhen Hua Li, Yanying Zhao, Xuming Zheng, and Kangnian Fan
The Journal of Physical Chemistry A 2011 Volume 115(Issue 24) pp:6551-6558
Publication Date(Web):May 23, 2011
DOI:10.1021/jp203352e
The reactions of titanium oxide molecules with dinitrogen have been studied by matrix isolation infrared spectroscopy. The titanium monoxide molecule reacts with dinitrogen to form the TiO(N2)x (x = 1–4) complexes spontaneously on annealing in solid neon. The TiO(η1-NN) complex is end-on bonded and was predicted to have a 3A′′ ground state arising from the 3Δ ground state of TiO. Argon doping experiments indicate that TiO(η1-NN) is able to form complexes with one or more argon atoms. Argon atom coordination induces a large red-shift of the N–N stretching frequency. The TiO(η2-N2)2 complex was characterized to have C2v symmetry, in which both the N2 ligands are side-on bonded to the titanium metal center. The tridinitrogen complex TiO(η1-NN)3 most likely has C3v symmetry with three end-on bonded N2 ligands. The TiO(η1-NN)4 complex was determined to have a C4v structure with four equivalent end-on bonded N2 ligands. In addition, evidence is also presented for the formation of the TiO2(η1-NN)x (x = 1–4) complexes, which were predicted to be end-on bonded.
Co-reporter:Mingfei Zhou, Jia Zhuang, Guanjun Wang, and Mohua Chen
The Journal of Physical Chemistry A 2011 Volume 115(Issue 11) pp:2238-2246
Publication Date(Web):February 28, 2011
DOI:10.1021/jp200143y
The reactions of molecular tantalum and niobium monoxides and dioxides with water were investigated by matrix isolation infrared spectroscopy. In solid neon, the metal monoxide and dioxide molecules reacted with water to form the MO(H2O) and MO2(H2O) (M = Ta, Nb) complexes spontaneously on annealing. The MO(H2O) complexes photochemically rearranged to the more stable HMO(OH) isomers via one hydrogen atom transfer from water to the metal center under visible light excitation. In contrast, the MO2(H2O) complexes isomerized to the more stable MO(OH)2 molecules via a hydrogen atom transfer from water to one of the oxygen atoms of metal dioxide upon visible light irradiation. The aforementioned species were identified by isotopic-substituted experiments as well as density functional calculations.
Co-reporter:Guanjun Wang, Jia Zhuang, and Mingfei Zhou
The Journal of Physical Chemistry A 2011 Volume 115(Issue 31) pp:8623-8629
Publication Date(Web):July 11, 2011
DOI:10.1021/jp204359a
The reactions of tantalum monoxide (TaO) and dioxide (TaO2) molecules with methanol in solid neon were investigated by infrared absorption spectroscopy. The ground-state TaO molecule reacted with CH3OH in forming the CH3OTa(O)H molecule via the hydroxylic hydrogen atom transfer from methanol to the metal center spontaneously on annealing. The observation of the spontaneous reaction is consistent with theoretical predictions that the OH bond activation process is both thermodynamically exothermic and kinetically facile. In contrast, the TaO2 molecule reacted with CH3OH to give primarily the TaO2(CH3OH) complex, which further rearranged to the CH3OTa(O)OH isomer via the hydroxylic hydrogen atom transfer from methanol to one of oxygen atom of metal dioxide upon visible light excitation.
Co-reporter:Chaoyang Zhang, Yuzhen Li, Ying Xiong, Xiaolin Wang, and Mingfei Zhou
The Journal of Physical Chemistry A 2011 Volume 115(Issue 43) pp:11971-11978
Publication Date(Web):September 20, 2011
DOI:10.1021/jp204698b
The stored and wasted explosives are usually in an acid or alkali environment, leading to the importance of exploring the acid and alkali effects on the decomposition mechanism of explosives. The acid and alkali effects on the decomposition of HMX molecule in gaseous state and in aqueous solution at 298 K are studied using quantum chemistry and molecular force field calculations. The results show that both H+ and OH– make the decomposition in gaseous state energetically favorable. However, the effect of H+ is much different from that of OH– in aqueous solution: OH– can accelerate the decomposition but H+ cannot. The difference is mainly caused by the large aqueous solvation energy difference between H+ and OH–. The results confirm that the dissociation of HMX is energetically favored only in the base solutions, in good agreement with previous HMX base hydrolysis experimental observations. The different acid and alkali effects on the HMX decomposition are dominated by the large aqueous solvation energy difference between H+ and OH–.
Co-reporter:Mingfei Zhou, Caixia Wang, Jia Zhuang, Yanying Zhao, and Xuming Zheng
The Journal of Physical Chemistry A 2011 Volume 115(Issue 1) pp:39-46
Publication Date(Web):December 13, 2010
DOI:10.1021/jp109498b
The reactions of group V metal dioxide molecules with dihydrogen have been studied by matrix isolation infrared spectroscopy. The ground state VO2 molecule is able to cleave dihydrogen heterolytically and spontaneously in forming the HVO(OH) molecule in solid argon. In contrast, the reaction of VO2 with dideuterium to form DVO(OD) proceeds only under UV−visible excitation via a weakly bound VO2(η2-D2) complex. Theoretical calculations predict that the dihydrogen cleavage process is thermodynamically exothermic with a small barrier. The niobium and tantalum dioxide molecules react with dihydrogen to give primarily the side-on bonded metal dioxide bis-dihydrogen complexes, NbO2(η2-H2)2 and TaO2(η2-H2)2, which are further transferred to the HNbO(OH) and HTaO(OH) molecules via photoisomerization in combination with H2 elimination under UV−visible light excitation.
Co-reporter:Chaoxian Chi, Hua Xie, Yuzhen Li, Ran Cong, Mingfei Zhou, and Zichao Tang
The Journal of Physical Chemistry A 2011 Volume 115(Issue 21) pp:5380-5386
Publication Date(Web):May 9, 2011
DOI:10.1021/jp202497x
The photoelectron images of Ag–(H2O)x (x = 1,2) and AgOH–(H2O)y (y = 0–4) are reported. The Ag–(H2O)1,2 anionic complexes have similar characteristics to the other two coinage metal–water complexes that can be characterized as metal atomic anion solvated by water molecules with the electron mainly localized on the metal. The vibrationally well-resolved photoelectron spectrum allows the adiabatic detachment energy (ADE) and vertical detachment energy (VDE) of AgOH– to be determined as 1.18(2) and 1.24(2) eV, respectively. The AgOH– anion interacts more strongly with water molecules than the Ag– anion. The photoelectron spectra of Ag–(H2O)x and AgOH–(H2O)y show a gradual increase in ADE and VDE with increasing x and y due to the solvent stabilization.
Co-reporter:Zijian Zhou, Yuzhen Li, Jia Zhuang, Guanjun Wang, Mohua Chen, Yanying Zhao, Xuming Zheng, and Mingfei Zhou
The Journal of Physical Chemistry A 2011 Volume 115(Issue 35) pp:9947-9953
Publication Date(Web):August 1, 2011
DOI:10.1021/jp205805a
The reactions of beryllium atoms with dioxygen were reinvestigated by matrix isolation infrared absorption spectroscopy. Besides the previously reported linear OBeO and cyclic Be2O2 molecules, two interconvertible beryllium ozonide complexes were prepared and characterized. The BeOBe(η2-O3) complex was formed on annealing, which is characterized to be a side-on bonded ozonide complex with a planar C2v structure. The BeOBe(η2-O3) complex isomerized to the BeOBe(η1-O3) isomer under visible light excitation, which is an end-on bonded ozonide complex with planar Cs symmetry. These two isomers are interconvertible; that is, visible light induces the conversion of the side-on bonded complex to the end-on bonded isomer, and vice versa on annealing. In addition, evidence is also presented for the linear BeOBeOBe cluster.
Co-reporter:Yu Gong, Mingfei Zhou
Chemical Physics Letters 2010 Volume 489(4–6) pp:181-186
Publication Date(Web):9 April 2010
DOI:10.1016/j.cplett.2010.02.077
Co-reporter:Dr. Mingfei Zhou;Caixia Wang;Dr. Zhen hua Li;Jia Zhuang;Dr. Yanying Zhao;Dr. Xuming Zheng;Dr. Kangnian Fan
Angewandte Chemie International Edition 2010 Volume 49( Issue 42) pp:7757-7761
Publication Date(Web):
DOI:10.1002/anie.201003001
Co-reporter:Yu Gong Dr.
ChemPhysChem 2010 Volume 11( Issue 9) pp:1888-1894
Publication Date(Web):
DOI:10.1002/cphc.201000104
Abstract
The interactions of water molecule with platinum dioxygen complex and dioxide molecule are investigated by means of matrix isolation infrared spectroscopy and density functional calculations. The platinum atoms reacted with dioxygen to form the previously reported Pt(O2) complex. The Pt(O2) complex reacted with water molecule to give the Pt(O2)–H2O complex, which was characterized to involve hydrogen bonding between one O atom of Pt(O2) and one H atom of H2O (structure A). Upon visible light irradiation, the hydrogen bonded Pt(O2)⋅⋅⋅HOH complex rearranged to another Pt(O2)–H2O isomer (structure B), which involves (O2)Pt⋅⋅⋅OH2 interaction. The Pt(O2)–H2O complex in structure B can be isomerized to the weakly bound platinum dioxide-water complex (structure C) under UV irradiation.
Co-reporter:Guanjun Wang, Yu Gong, QingQing Zhang, and Mingfei Zhou
The Journal of Physical Chemistry A 2010 Volume 114(Issue 40) pp:10803-10809
Publication Date(Web):September 21, 2010
DOI:10.1021/jp107434f
The reactions of magnesium atoms with dioxygen and dioxygen/carbon monoxide mixture have been investigated by matrix isolation infrared absorption spectroscopy. Magnesium atoms react with dioxygen in solid argon to form the inserted MgO2 molecules under UV excitation, which were previously characterized. Annealing allows the dioxygen molecules to diffuse and to react with MgO2 and form the magnesium bisozonide complex, Mg(O3)2, which is proposed to be coordinated by two argon atoms in solid argon matrix. The Mg(O3)2(Ar)2 complex is characterized to have two equivalent side-on bonded ozonide ligands with a D2h symmetry. The coordinated argon atoms can be replaced by carbon monoxide to give the magnesium bisozonide dicarbonyl complex, Mg(O3)2(CO)2, a neutral magnesium carbonyl complex with CO binding to the Mg2+ center.
Co-reporter:Guanjun Wang;Jing Su;Yu Gong Dr.;Jun Li Dr.
Angewandte Chemie International Edition 2010 Volume 49( Issue 7) pp:1302-1305
Publication Date(Web):
DOI:10.1002/anie.200906473
Co-reporter:Guanjun Wang;Jing Su;Yu Gong Dr.;Jun Li Dr.
Angewandte Chemie 2010 Volume 122( Issue 7) pp:1324-1327
Publication Date(Web):
DOI:10.1002/ange.200906473
Co-reporter:Dr. Mingfei Zhou;Caixia Wang;Dr. Zhen hua Li;Jia Zhuang;Dr. Yanying Zhao;Dr. Xuming Zheng;Dr. Kangnian Fan
Angewandte Chemie 2010 Volume 122( Issue 42) pp:7923-7927
Publication Date(Web):
DOI:10.1002/ange.201003001
Co-reporter:Yongfei Huang, Yanying Zhao, Xuming Zheng and Mingfei Zhou
The Journal of Physical Chemistry A 2010 Volume 114(Issue 7) pp:2476-2482
Publication Date(Web):February 3, 2010
DOI:10.1021/jp9101948
Reactions of scandium and yttrium monoxide molecules (ScO and YO) with monochloromethane have been studied in solid argon by infrared absorption spectroscopy and density functional theoretical calculations. The metal monoxide molecules were prepared by laser-evaporation of bulk metal oxide targets. The results show that the ground state scandium and yttrium monoxide molecules reacted with CH3Cl to form two MO(CH3Cl) (M = Sc, Y) complex isomers spontaneously on annealing. Broad-band UV−visible irradiation initiated the addition of the Cl−C bond to the M═O bond to form the CH3OMCl molecule and the addition of the C−H bond to the M═O bond to give the CH2ClMOH isomer, both of which are more stable than the MO(CH3Cl) complex structures. The CH2ClMOH molecule was predicted to involve agnostic interaction between the chlorine atom and the metal atom.
Co-reporter:YanYing Zhao
Science China Chemistry 2010 Volume 53( Issue 2) pp:327-336
Publication Date(Web):2010 February
DOI:10.1007/s11426-010-0044-9
In this review, we summarize our recent results on matrix isolation infrared spectroscopic studies and theoretical investigations of noble gas-transition metal oxide complexes. The results show that some transition metal oxide species trapped in solid noble gas matrices are chemically coordinated by one or multiple noble gas atoms forming noble gas complexes and, hence, cannot be regarded as isolated species. Noble gas coordination alters the vibrational frequencies as well as the geometric and electronic structures of transition metal oxide species trapped in solid noble gas matrixes. The interactions between noble gas atoms and transition metal oxides involve ion-induced dipole interactions as well as chemical bonding interactions. Periodic trends in the bonding in these noble gas-transition metal complexes are discussed.
Co-reporter:Yanying Zhao, Yongfei Huang, Xuming Zheng and Mingfei Zhou
The Journal of Physical Chemistry A 2010 Volume 114(Issue 18) pp:5779-5786
Publication Date(Web):April 20, 2010
DOI:10.1021/jp102199c
Reactions of niobium and tantalum monoxide and dioxide molecules with monochloromethane in solid argon have been investigated by infrared absorption spectroscopy and density functional theoretical calculations. The results show that the ground-state MOx (M = Nb, Ta, x = 1, 2) molecules react with CH3Cl to form the weakly bound MO(CH3Cl) and MO2(CH3Cl) complexes. The MO(CH3Cl) complexes rearrange to the more stable CH2ClM(O)H isomer upon visible light excitation, whereas the MO2(CH3Cl) complexes isomerize to the more stable CH2ClM(O)OH molecules under ultraviolet light irradiation. The CH2ClM(O)H and CH2ClM(O)OH molecules were predicted to involve agostic interactions between the chlorine atom and the metal center.
Co-reporter:Caixia Wang, Jia Zhuang, Guanjun Wang, Mohua Chen, Yanying Zhao, Xuming Zheng and Mingfei Zhou
The Journal of Physical Chemistry A 2010 Volume 114(Issue 31) pp:8083-8089
Publication Date(Web):July 20, 2010
DOI:10.1021/jp103866r
The reaction of tantalum dioxide molecule with dinitrogen has been studied by matrix isolation infrared spectroscopy. The tantalum dioxide molecules produced from laser evaporation of bulk Ta2O5 target reacted with dinitrogen to form the TaO2(η1-NN)x (x = 1−3) complexes on annealing, in which the N2 ligands are end-on bonded to the tantalum metal center. The TaO2(η1-NN)3 complex decomposed to TaO2(η1-NN)2 under infrared irradiation. The TaO2(η1-NN)2 and TaO2(η1-NN)3 complexes rearranged to the less stable TaO2(η1-NN)(η2-N2) and TaO2((η1-NN)2(η2-N2) isomers under visible light excitation. Both the mono- and bis-dinitrogen complexes were predicted to have 2A′ or 2A1 ground states arising from the 2A1 ground state of TaO2, whereas the two tridinitrogen complexes were predicted to have 2B2 ground states with C2v symmetry, which are derived from the 2B1 excited state of TaO2.
Co-reporter:Yu Gong and Mingfei Zhou, Lester Andrews
Chemical Reviews 2009 Volume 109(Issue 12) pp:6765
Publication Date(Web):September 17, 2009
DOI:10.1021/cr900185x
Co-reporter:Yu Gong and Mingfei Zhou
Physical Chemistry Chemical Physics 2009 vol. 11(Issue 39) pp:8714-8720
Publication Date(Web):31 Jul 2009
DOI:10.1039/B909999A
Matrix isolation infrared spectra and quantum chemical calculations of the copper dioxygen/ozonide complexes, CuO5, CuO4 and CuO4− are reported. These oxygen-rich species were prepared by reactions of laser-evaporated copper atoms with dioxygen or ozone in solid argon. The CuO5 complex was determined to be a superoxo copper ozonide complex, in which both the superoxo and ozonide ligands are side-on bonded to the copper center. It was predicted to have a 4A1 ground state with planar C2v symmetry. Besides CuO5, the previously observed CuO4 complex and a new CuO4− anion were also formed. The CuO4 complex was characterized to be a side-on bonded copper disuperoxide complex, which has a 4B2u ground state with planar D2h symmetry. The CuO4− anion was characterized to be a disuperoxide complex with both superoxide ligands coordinated to the Cu center in an end-on fashion having a 3Au ground state with planar C2h symmetry.
Co-reporter:Renhu Ma, Dongmei Yuan, Mohua Chen and Mingfei Zhou
The Journal of Physical Chemistry A 2009 Volume 113(Issue 7) pp:1250-1254
Publication Date(Web):January 13, 2009
DOI:10.1021/jp8083293
The infrared spectrum of the nitrobenzene anion isolated in solid argon is presented. The nitrobenzene anion was prepared by co-deposition of a nitrobenzene/Ar mixture with high-frequency discharged argon at 4 K. Photosensitive absorptions are assigned to different vibrational modes of the nitrobenzene anion on the basis of isotopic substitutions (15N and deuterium), as well as theoretical calculations. The anion loses one electron to give the neutral nitrobenzene upon visible light (500 < λ < 600 nm) irradiation. Theoretical calculations predicated that the anion has a planar C2v symmetry with a shorter C−N bond and longer N−O bonds relative to those of neutral nitrobenzene.
Co-reporter:Yu Gong and Mingfei Zhou
The Journal of Physical Chemistry A 2009 Volume 113(Issue 17) pp:4990-4995
Publication Date(Web):March 31, 2009
DOI:10.1021/jp900974w
Transition-metal dioxide anions RhO2−, IrO2−, PtO2−, and AuO2− were produced from cocondensation of laser-ablated metal atoms and electrons with dioxygen in excess argon at 6 K. Photosensitive absorptions were assigned to the antisymmetric stretching vibration (ν3) of the metal dioxide anions from isotopic shifts and splittings as well as theoretical frequency calculations. On the basis of the observed ν3 vibrational frequencies for M16O2 and M18O2, the anions are estimated to be linear or near linear. Density functional calculations at the DFT/B3LYP level predicted that the third-row transition-metal dioxide anions IrO2−, PtO2−, and AuO2− have singlet, doublet, and triplet ground states with linear structures, while the RhO2− anion was predicted to have a slightly bent geometry.
Co-reporter:Yu Gong, Chuanfan Ding and Mingfei Zhou
The Journal of Physical Chemistry A 2009 Volume 113(Issue 30) pp:8569-8576
Publication Date(Web):July 6, 2009
DOI:10.1021/jp905428s
The reactions of yttrium and lanthanum atoms with O2 have been reinvestigated using matrix isolation infrared spectroscopy and theoretical calculations. The ground-state yttrium and lanthanum atoms react with O2 to produce the inserted yttrium and lanthanum dioxide molecules as the initial products. The yttrium dioxide molecule interacts spontaneously with additional O2 molecules to form the oxygen-rich OY(η2-O3) complex and possibly the (η2-O2)Y(η2-O3)2 complexes upon sample annealing, which can be regarded as the side-on bonded yttrium monoxide ozonide complex and the superoxo yttrium bisozonide complex, respectively. Visible irradiation induces the isomerization of the OY(η2-O3) complex to the superoxo yttrium peroxide Y(η2-O2)2 isomer, in which both the superoxo and peroxo ligands are side-on bonded to the yttrium center. The lanthanum dioxide molecule reacts with additional O2 molecules to form the lanthanum dioxide−dioxygen complex with planar C2v symmetry, which rearranges to the lanthanum monoxide ozonide complex, OLa(η2-O3), under near-infrared excitation.
Co-reporter:Renhu Ma, Mohua Chen and Mingfei Zhou
The Journal of Physical Chemistry A 2009 Volume 113(Issue 46) pp:12926-12931
Publication Date(Web):October 9, 2009
DOI:10.1021/jp9084266
Infrared spectra of chloromethyl and bromomethyl cations isolated in solid argon are reported. Cocondensation of dichloromethane and dibromomethane with high-frequency discharged argon at 4 K produces the dichloromethane and dibromomethane cations, which dissociate upon visible light irradiation to form the chloromethyl and bromomethyl cations. On the basis of isotopic substitutions (13C and deuterium) as well as theoretical frequency calculations, photosensitive absorptions are assigned to different vibrational modes of the chloromethyl and bromomethyl cations. Theoretical calculations predict that the halomethyl cations have a planar C2v symmetry with a shorter C−X bond and longer C−H bonds relative to those of the halomethyl free radicals.
Co-reporter:Yu Gong, Guanjun Wang and Mingfei Zhou
The Journal of Physical Chemistry A 2009 Volume 113(Issue 18) pp:5355-5359
Publication Date(Web):April 14, 2009
DOI:10.1021/jp902166x
The copper atom reacts with dioxygen in solid argon to form a mononuclear copper dioxygen complex Cu(η2-O2)(η1-O2)2 bearing both side-on and end-on bonded O2 ligands. The complex is characterized as being a trisuperoxide species with the copper center in its unusual +3 oxidation state. The Cu(III) trisuperoxide complex loses an end-on bonded superoxo ligand in forming the copper bisdioxygen complex under infrared irradiation.
Co-reporter:Yu Gong Dr.;Martin Kaupp Dr.;Sebastian Riedel Dr.
Angewandte Chemie 2009 Volume 121( Issue 42) pp:
Publication Date(Web):
DOI:10.1002/ange.200904022
Co-reporter:Yu Gong Dr.;Martin Kaupp Dr.;Sebastian Riedel Dr.
Angewandte Chemie International Edition 2009 Volume 48( Issue 42) pp:7879-7883
Publication Date(Web):
DOI:10.1002/anie.200902733
Co-reporter:Yu Gong Dr.;Martin Kaupp Dr.;Sebastian Riedel Dr.
Angewandte Chemie International Edition 2009 Volume 48( Issue 42) pp:
Publication Date(Web):
DOI:10.1002/anie.200904022
Co-reporter:Renhu Ma, Dongmei Yuan, Mohua Chen, Mingfei Zhou, Xuefeng Wang and Lester Andrews
The Journal of Physical Chemistry A 2009 Volume 113(Issue 17) pp:4976-4981
Publication Date(Web):March 30, 2009
DOI:10.1021/jp9001687
Cocondensation of carbon disulfide with high-frequency discharged argon at 4 K produced carbon monosulfide and atomic sulfur, which reacted spontaneously upon annealing to form the carbon trisulfide molecule as identified from the multiplets observed in mixed 12C, 13C and 32S, 34S isotopic spectra. On the basis of isotopic substitution and theoretical frequency calculations, infrared absorptions at 1263.3 and 570.1 cm−1 were assigned to predominantly C═S stretching and bending vibrations of CS3 in solid argon. The CS3 molecule, which was calculated to have a singlet ground state with C2v symmetry, dissociated to form the weakly bound SCS−S complex upon visible light irradiation.
Co-reporter:Yu Gong Dr.;Martin Kaupp Dr.;Sebastian Riedel Dr.
Angewandte Chemie 2009 Volume 121( Issue 42) pp:8019-8023
Publication Date(Web):
DOI:10.1002/ange.200902733
Co-reporter:Mingfei Zhou, Renhu Ma, Dongmei Yuan and Mohua Chen
The Journal of Physical Chemistry A 2009 Volume 113(Issue 12) pp:2826-2830
Publication Date(Web):February 18, 2009
DOI:10.1021/jp809683n
The reaction of chloromethyl radical with molecular oxygen in solid argon has been studied using matrix isolation infrared absorption spectroscopy. The chloromethyl radical was produced via codeposition of chloromethane with high frequency discharged argon atoms. The chloromethyl radical reacted with dioxygen spontaneously on annealing to form the chloromethylperoxy radical, which was characterized on the basis of isotopic splitting (Cl and O) as well as quantum chemical calculations. The chloromethylperoxy radical dissociated to give the weakly bound ClCO−H2O complex under UV light irradiation. The calculations predicted that the ClCO−H2O complex was produced by hydrogen atom transfer from a CHCl(O)−OH intermediate.
Co-reporter:Yanying Zhao, Xuming Zheng, Mingfei Zhou
Chemical Physics 2008 Volume 351(1–3) pp:13-18
Publication Date(Web):3 July 2008
DOI:10.1016/j.chemphys.2008.03.026
Abstract
The combination of matrix isolation infrared spectroscopic and quantum chemical calculation results indicate that the NbO2 molecule is coordinated by two noble gas atoms in forming the NbO2(Ng)2 (Ng = Ar, Xe) complexes in solid noble gas matrixes. In contrast, the TaO2 molecule is not able to form similar noble gas complex. The niobium and tantalum dioxides further react with dioxygen to form the side-on bonded superoxo-dioxide complexes MO4 (M = Nb, Ta), which are coordinated by one argon atom in solid argon matrix. The coordinated Ar atom in MO4(Ar) can be replaced by O2 or Xe in forming the MO6 and MO4(Xe) complexes. The results indicate that the NbO2, NbO4 and TaO4 molecules trapped in solid noble gas matrixes should be regarded as the NbO2(Ng)2 and MO4(Ng) (Ng = Ar, Xe; M = Nb, Ta) complexes instead of “isolated” metal oxide species.
Co-reporter:Yu Gong and Mingfei Zhou
The Journal of Physical Chemistry A 2008 Volume 112(Issue 25) pp:5670-5675
Publication Date(Web):May 30, 2008
DOI:10.1021/jp8014172
The reaction of boron dioxide with water molecule has been studied using matrix isolation infrared spectroscopy. The boron dioxide molecules produced by codeposition of laser-evaporated boron atoms with dioxygen react spontaneously with water molecules to form OB(OH)2, which is characterized to have a doublet ground-state with two OH groups in the cis−trans form. Isotopic substitution results indicate that the hydrolysis process proceeds via a concerted two hydrogen atom transfer mechanism. The cis−trans-OB(OH)2 molecule is photosensitive; it decomposes to the OH·OB(OH) complex upon broadband UV−visible irradiation. The OH·OB(OH) complex is determined to have a 2A′′ ground-state with a bent Cs symmetry, in which the terminal oxygen atom of the OB(OH) fragment is hydrogen bonded with the hydroxyl radical. The OH·OB(OH) complex recombines to the cis−trans-OB(OH)2 molecule upon sample annealing.
Co-reporter:Mohua Chen, Rongjing Yang, Renhu Ma and Mingfei Zhou
The Journal of Physical Chemistry A 2008 Volume 112(Issue 31) pp:7157-7161
Publication Date(Web):July 17, 2008
DOI:10.1021/jp803436m
UV light irradiation of dimethyl sulfoxide (DMSO) in low temperature solid argon matrix produces sulfenic ester, CH3SOCH3, a high energy structural isomer of DMSO. The sulfenic ester molecule further dissociates to the CH2O−CH3SH complex under 266 nm laser irradiation. The CH2S−CH3OH complex is also formed upon UV light irradiation. The infrared spectra of the aforementioned species are assigned on the basis of isotopic substitutions (13C and deuterium) as well as density functional frequency calculations.
Co-reporter:Yanying Zhao, Jing Su, Yu Gong, Jun Li and Mingfei Zhou
The Journal of Physical Chemistry A 2008 Volume 112(Issue 37) pp:8606-8611
Publication Date(Web):August 27, 2008
DOI:10.1021/jp804995d
Laser-evaporated chromium atoms are shown to insert into dioxygen to form CrO2 in solid argon. Annealing allows diffusion and reactions to form (η2-O2)2CrO2, which is characterized as [(O2−)2(CrO2)2+], a side-on bonded disuperoxo−chromium dioxide complex. The (η2-O2)2CrO2 complex further reacts with xenon atom doped in solid argon to give (η1-OO)(η2-O2)CrO2(Xe), which can be regarded as an O2 molecule weakly interacting with [(O2)2−(CrO2)2+Xe], a side-on bonded peroxo−chromium dioxide-xenon complex. The results indicate surprisingly that xenon atom induces a disproportionation reaction from superoxo to peroxo and dioxygen complex.
Co-reporter:Yu Gong and Mingfei Zhou
The Journal of Physical Chemistry A 2008 Volume 112(Issue 40) pp:9758-9762
Publication Date(Web):September 11, 2008
DOI:10.1021/jp805495d
The reaction of titanium monoxide molecules and O2 was studied by using matrix isolation infrared spectroscopy as well as theoretical calculations. The titanium monoxide molecule reacts with O2 to form TiO3 spontaneously on annealing. The TiO3 molecule is characterized to be a side-on bonded peroxo titanium monoxide complex, (η2-O2)TiO, which has a nonplanar Cs symmetry with a 1A′ ground state. The (η2-O2)TiO complex can further coordinate another dioxygen to give TiO5, a disuperoxo titanium monoxide complex, (η2-O2)2TiO, which possesses a 3A′′ ground state and a nonplanar Cs geometry.
Co-reporter:Yu Gong and Mingfei Zhou
The Journal of Physical Chemistry A 2008 Volume 112(Issue 43) pp:10838-10842
Publication Date(Web):October 2, 2008
DOI:10.1021/jp806442y
Two FeO3 isomers were prepared and characterized using matrix isolation infrared spectroscopy and theoretical calculations. The iron monoxide molecules produced from laser evaporation of the bulk iron oxide target react with dioxygen in solid argon to form the (η2-O2)FeO complex spontaneously on annealing. The (η2-O2)FeO complex was predicted to have a 5B2 ground state with a planar C2v structure, in which the O2 fragment is side-on bonded to the iron center. The (η2-O2)FeO complex rearranges to the more stable iron trioxide isomer upon visible light (λ > 500 nm) irradiation. The iron trioxide molecule was predicted to have a closed-shell singlet ground state with a planar D3h symmetry, in which the iron possesses a +6 oxidation state.
Co-reporter:Zhen Hua Li, Yu Gong, Kangnian Fan and Mingfei Zhou
The Journal of Physical Chemistry A 2008 Volume 112(Issue 51) pp:13641-13649
Publication Date(Web):November 18, 2008
DOI:10.1021/jp806990k
FeO2− anions were produced by co-condensation of laser-ablated iron atoms and electrons with dioxygen in excess argon at 6 K. A photosensitive absorption at 870.6 cm−1 is assigned to the antisymmetric OFeO stretching vibration (ν3) of the inserted FeO2− anion trapped in solid argon. On the basis of the observed ν3 vibrational frequencies for Fe16O2 and Fe18O2, the anion is estimated to be linear. Due to the severe symmetry-breaking problems of the reference wave function, calculations with single-reference methods, including various DFT and post-HF methods, are unreliable for this molecule. However, the state-averaged multireference MRCI method, which incorporates both dynamical and nondynamical correlations, predicted that the anion has a linear doublet ground state, consistent with the experimental observations.
Co-reporter:Yu Gong, Guanjun Wang and Mingfei Zhou
The Journal of Physical Chemistry A 2008 Volume 112(Issue 22) pp:4936-4941
Publication Date(Web):May 13, 2008
DOI:10.1021/jp800955e
A manganese atom reacts with dioxygen to form the previously characterized MnO2 molecule in solid argon under UV−visible light irradiation. Subsequent sample annealing allows the dioxygen molecules to diffuse and to react with MnO2 to give the (η2-O2)MnO2 complex, which is characterized to be a side-on bonded peroxo manganese dioxide complex. The manganese tetraoxide MnO4, which was predicted to be less stable than the (η2-O2)MnO2 isomer, was not observed. However, the (η2-O2)MnO2 complex reacts with another weakly coordinated dioxygen to give the (η2-O2)MnO4 complex via visible light irradiation, in which the manganese tetraoxide is coordinated and stabilized by a side-on bonded O2 molecule. Manganese dimer reacts with dioxygen to form the cyclic Mn(μ-O)2Mn cluster spontaneously upon annealing, which further reacts with dioxygen to give the (η2-O2)2Mn(μ-O)2Mn cluster, a side-on bonded disuperoxide complex with a planar D2h structure.
Co-reporter:Mingfei Zhou Dr.;Xi Jin;Yu Gong;Jun Li Dr.
Angewandte Chemie International Edition 2007 Volume 46(Issue 16) pp:
Publication Date(Web):9 MAR 2007
DOI:10.1002/anie.200605218
Building up from scratch: The Gd2 molecule reacts with N2 in solid argon to form a homoleptic dinuclear dinitrogen complex containing a drastically activated side-on and end-on bonded N2 ligand (see scheme; Gd orange, N blue). The complex rearranges to a planar cyclic [Gd(μ-N)2Gd] isomer with a completely cleaved NN bond, which further dimerizes to form a cubic [Gd4N4] cluster, a building block for (GdN)x nanoparticles.
Co-reporter:Mingfei Zhou Dr.;Xi Jin;Yu Gong;Jun Li Dr.
Angewandte Chemie 2007 Volume 119(Issue 16) pp:
Publication Date(Web):9 MAR 2007
DOI:10.1002/ange.200605218
Von Grund auf: Gd2-Moleküle reagieren mit N2 in festem Argon zu einem homoleptischen Distickstoff-Zweikernkomplex mit stark aktiviertem side-on- und end-on-gebundenem N2-Liganden (siehe Schema; Gd orange, N blau). Der Komplex lagert sich in das planare cyclische Isomer [Gd(μ-N)2Gd] um, in dem keine N-N-Bindung mehr vorliegt; diese Spezies dimerisiert zu dem würfelförmigen Cluster [Gd4N4], der als Baustein in (GdN)x-Nanopartikeln auftritt.
Co-reporter:Yaqiong Wang, Yu Gong, Xuming Zheng, Mingfei Zhou
Chemical Physics Letters 2006 Volume 431(1–3) pp:13-18
Publication Date(Web):11 November 2006
DOI:10.1016/j.cplett.2006.09.040
Dinitrogen activation by titanium benzene complex has been studied by matrix isolation infrared spectroscopy and density functional theoretical calculations. The ground state titanium atoms react with dinitrogen and benzene mixtures in solid argon to form the end-on bonded Ti(η6-C6H6)(η1-NN) and Ti(η6-C6H6)(η1-NN)2 complexes spontaneously on annealing. These complexes rearrange to the side-on bonded Ti(η6-C6H6)(η2-N2) and Ti(η6-C6H6)(η1-NN)(η2-N2) molecules with a more activated N2 upon red light irradiation.Titanium atoms react with dinitrogen and benzene mixtures in solid argon to form the end-on bonded Ti(η6-C6H6)(η1-NN) and Ti(η6-C6H6)(η1-NN)2 complexes, which photochemically rearrange to the side-on bonded Ti(η6-C6H6)(η2-N2) and Ti(η6-C6H6)(η1-NN)(η2-N2) isomers with a more activated N2.
Co-reporter:Mingfei Zhou ;Ling Jiang;Qiang Xu Dr.
Chemistry - A European Journal 2004 Volume 10(Issue 22) pp:
Publication Date(Web):7 OCT 2004
DOI:10.1002/chem.200400474
Reactions of boron atoms with CO molecules in solid argon form the following boron carbonyl species (which have been reported earlier): BCO, BBCO, OCBBCO, B(CO)2, and B4(CO)2. The OCBBCO molecule underwent a photochemical rearrangement where CO was activated to form the OBBCCO and OBCCBO molecules. The new molecules were identified on the basis of isotopic IR studies with 10B, 11B, 13C16O, 12C18O, and carbon dioxide mixtures in addition to comparison with quantum-chemical calculations of isotopic frequencies. Theoretical analyses showed that the OBBCCO and OBCCBO molecules are linear with CC double and triple bonding, respectively, and lie at a much lower energy than the linear OCBBCO structure.
Co-reporter:Jiwen Jian, Wei Li, Xuan Wu and Mingfei Zhou
Chemical Science (2010-Present) 2017 - vol. 8(Issue 6) pp:
Publication Date(Web):
DOI:10.1039/C7SC01399J
Co-reporter:Wenhua Xu, Xi Jin, Mohua Chen, Pekka Pyykkö, Mingfei Zhou and Jun Li
Chemical Science (2010-Present) 2012 - vol. 3(Issue 5) pp:NaN1554-1554
Publication Date(Web):2012/02/22
DOI:10.1039/C2SC00998F
The reactions of Group-3 metal atoms with carbon monoxide in solid argon have been studied using matrix isolation infrared absorption spectroscopy. The lanthanide monocarbonyls LnCO were produced spontaneously on annealing. The observations on LnCO, Ln = Pr, Nd, Sm, Eu, Tb, Dy, Ho, and Er are new. We also theoretically study the structure, bonding, and C–O stretch infrared frequencies. The covalent M–C bonding contains both M ← C σ donation from the carbon lone pair, and M 5d → CO 2π* back donation contributions. In addition to the open 4fn shells, the total spin, as found earlier, may have contributions from an M ‘σ doughnut’ and the M–C π bond, in a σ1π1, σ1π2 high-spin, or σ2π1 low-spin configuration. They form at least a single-bond, and those with the σ1π2 configuration approach a double bond in length. The weakening of the C–O bonding is related to the back donation to the antibonding C–O 2π* orbital.
Co-reporter:Chaoxian Chi, Jieming Cui, Zhen Hua Li, Xiaopeng Xing, Guanjun Wang and Mingfei Zhou
Chemical Science (2010-Present) 2012 - vol. 3(Issue 5) pp:NaN1706-1706
Publication Date(Web):2012/02/29
DOI:10.1039/C2SC20119D
Infrared spectra of mass-selected homoleptic dinuclear iron carbonyl cluster anions Fe2(CO)n− (n = 4–9) are measured via infrared photodissociation spectroscopy in the carbonyl stretching frequency region. The cluster anions are produced via a laser vaporization supersonic cluster source. Density functional calculations have been performed and the calculated vibrational spectra are compared to the experimental data to identify the gas-phase structures of the cluster anions. The experimentally observed Fe2(CO)n− (n = 4–7) cluster anions are characterized to have unusual asymmetric (OC)4Fe–Fe(CO)n−4 structures, which also correspond to the computed lowest energy structures. The experimentally observed Fe2(CO)8− cluster anion is determined to have an unbridged structure instead of the previously reported dibridged structure. The Fe2(CO)9− cluster anion is determined to involve a Fe2(CO)8− core anion that is solvated by an external CO molecule. Bonding analysis indicates that these anions each have a Fe–Fe single bond to satisfy the 18-electron configuration of one iron center. The results provide important new insight into the structure and bonding mechanisms of transition-metal carbonyl clusters.
Co-reporter:Guanjun Wang, Jieming Cui, Chaoxian Chi, Xiaojie Zhou, Zhen Hua Li, Xiaopeng Xing and Mingfei Zhou
Chemical Science (2010-Present) 2012 - vol. 3(Issue 11) pp:NaN3279-3279
Publication Date(Web):2012/08/15
DOI:10.1039/C2SC20947K
Infrared spectra of mass-selected homoleptic iron carbonyl cluster cations including mononuclear Fe(CO)5+ and Fe(CO)6+, dinuclear Fe2(CO)8+ and Fe2(CO)9+, and trinuclear Fe3(CO)12+ are measured via infrared photodissociation spectroscopy in the carbonyl stretching frequency region. The structures are established by comparison of the experimental spectra with simulated spectra derived from density functional calculations. Only one IR band is observed for the Fe(CO)5+ cation, which is predicted to have a C4v structure. The Fe(CO)6+ cation is determined to be a weakly bound complex involving a Fe(CO)5+ core ion. In contrast to neutral clusters which have symmetric structures with two and three bridging carbonyl ligands, the dinuclear Fe2(CO)8+ and Fe2(CO)9+ cations are characterized to have unbridged asymmetric (OC)5Fe–Fe(CO)n+ (n = 3 and 4) structures. The trinuclear Fe3(CO)12+ cluster cation is determined to have an open chain like (OC)5Fe–Fe(CO)2–Fe(CO)5 structure instead of the triangular structure with two bridging CO groups for the Fe3(CO)12 neutral. The di- and trinuclear cluster cations all involve a square pyramid like Fe(CO)5 building block that satisfies the 18-electron configuration of this iron center. The Fe(CO)5 building block is isolobal to the CH3 fragment in hydrocarbon chemistry, the Fe2(CO)9+ and Fe3(CO)12+ cluster cations may be considered through isolobality to be metal carbonyl analogues of the ethyl and isopropyl cations.
Co-reporter:Lichen Wang, Guanjun Wang, Hui Qu, Zhen Hua Li and Mingfei Zhou
Physical Chemistry Chemical Physics 2014 - vol. 16(Issue 22) pp:
Publication Date(Web):
DOI:10.1039/C4CP00557K
Co-reporter:Jieming Cui, Guanjun Wang, Xiaojie Zhou, Chaoxian Chi, Zhen Hua Li, Zhipan Liu and Mingfei Zhou
Physical Chemistry Chemical Physics 2013 - vol. 15(Issue 25) pp:NaN10232-10232
Publication Date(Web):2013/02/04
DOI:10.1039/C3CP44588G
Infrared spectra of mass-selected homoleptic nickel carbonyl cluster cations including dinuclear Ni2(CO)7+ and Ni2(CO)8+, trinuclear Ni3(CO)9+ and tetranuclear Ni4(CO)11+ are measured via infrared photodissociation spectroscopy in the carbonyl stretching frequency region. The structures are established by comparison of the experimental spectra with simulated spectra derived from density functional calculations. The Ni2(CO)7+ cation is characterized to have an unbridged asymmetric (OC)4Ni–Ni(CO)3+ structure with a Ni–Ni single bond. The Ni2(CO)8+ cation has a Ni–Ni half-bonded D3d structure with both nickel centers exhibiting an 18-electron configuration. The trinuclear Ni3(CO)9+ cluster cation is determined to have an open chain like (OC)4Ni–NiCO–Ni(CO)4 structure. The tetranuclear Ni4(CO)11+ cluster cation is determined to have a tetrahedral structure with two-center and three-center bridge-bonded carbonyl units. These nickel carbonyl cluster cations all involve trigonal pyramid like Ni(CO)4 building blocks that satisfy the 18-electron configuration of the nickel centers.
Co-reporter:Yu Gong and Mingfei Zhou
Physical Chemistry Chemical Physics 2009 - vol. 11(Issue 39) pp:NaN8720-8720
Publication Date(Web):2009/07/31
DOI:10.1039/B909999A
Matrix isolation infrared spectra and quantum chemical calculations of the copper dioxygen/ozonide complexes, CuO5, CuO4 and CuO4− are reported. These oxygen-rich species were prepared by reactions of laser-evaporated copper atoms with dioxygen or ozone in solid argon. The CuO5 complex was determined to be a superoxo copper ozonide complex, in which both the superoxo and ozonide ligands are side-on bonded to the copper center. It was predicted to have a 4A1 ground state with planar C2v symmetry. Besides CuO5, the previously observed CuO4 complex and a new CuO4− anion were also formed. The CuO4 complex was characterized to be a side-on bonded copper disuperoxide complex, which has a 4B2u ground state with planar D2h symmetry. The CuO4− anion was characterized to be a disuperoxide complex with both superoxide ligands coordinated to the Cu center in an end-on fashion having a 3Au ground state with planar C2h symmetry.
Co-reporter:Shu-Xian Hu, Jiwen Jian, Jing Su, Xuan Wu, Jun Li and Mingfei Zhou
Chemical Science (2010-Present) 2017 - vol. 8(Issue 5) pp:NaN4043-4043
Publication Date(Web):2017/03/15
DOI:10.1039/C7SC00710H
The neutral molecule NPrO and its anion NPrO− are produced via co-condensation of laser-ablated praseodymium atoms with nitric oxide in a solid neon matrix. Combined infrared spectroscopy and state-of-the-art quantum chemical calculations confirm that both species are pentavalent praseodymium nitride-oxides with linear structures that contain PrN triple bonds and PrO double bonds. Electronic structure studies show that the neutral NPrO molecule features a 4f0 electron configuration and a Pr(V) oxidation state similar to that of the isoelectronic PrO2+ ion, while its NPrO− anion possesses a 4f1 electron configuration and a Pr(IV) oxidation state. The neutral NPrO molecule is thus a rare lanthanide nitride-oxide species with a Pr(V) oxidation state, which follows the recent identification of the first Pr(V) oxidation state in the PrO2+ and PrO4 complexes (Angew. Chem. Int. Ed., 2016, 55, 6896). This finding indicates that lanthanide compounds with oxidation states of higher than +IV are richer in chemistry than previously recognized.
Co-reporter:Jun-Bo Lu, Jiwen Jian, Wei Huang, Hailu Lin, Jun Li and Mingfei Zhou
Physical Chemistry Chemical Physics 2016 - vol. 18(Issue 45) pp:NaN31131-31131
Publication Date(Web):2016/10/19
DOI:10.1039/C6CP06753K
The experimentally known highest oxidation state of iron has been determined to be Fe(VI) so far. Here we report a combined matrix-isolation infrared spectroscopic and theoretical study of two interconvertible iron oxide anions: a dioxoiron peroxide complex [(η2-O2)FeO2]− with a C2v-structure and a tetroxide FeO4− with a D2d tetrahedral structure, which are formed by co-condensation of laser-ablated iron atoms and electrons with O2/Ar mixtures at 4 K. Quantum chemistry theoretical studies indicate that the Jahn–Teller distorted tetroxide FeO4− anion is a d1 species with hereto the highest iron formal oxidation state Fe(VII).
