Xiaoyan Li

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Name: 李晓燕; XiaoYan Li

Organization: Shandong University , China

Department: School of Chemistry and Chemical Engineering

Title: Professor(PhD)

TOPICS

Inorganic Chemistry

Organic Chemistry

C-H Activation

Chemicals
References

Vinyl/Phenyl Exchange Reaction within Vinyl Nickel Complexes Bearing Chelate [P, S]-Ligands

Co-reporter:Benjing Xue, Hongjian Sun, Shishuai Ren, Xiaoyan Li, and Olaf Fuhr

Organometallics November 13, 2017 Volume 36(Issue 21) pp:4246-4246

Publication Date(Web):October 25, 2017

DOI:10.1021/acs.organomet.7b00671

Three nickel(II) hydrides, [2-Ph2P(4-Me-C6H3)S]NiH(PMe3)2 (1), [2-Ph2P(6-Me3Si-C6H3)S]NiH(PMe3)2 (2), and [2-Ph2P(4-Me3Si -C6H3)S]NiH(PMe3)2 (3), were synthesized via S–H bond activation through the reaction of Ni(PMe3)4 with (2-diphenylphosphanyl)thiophenols. The reactions of nickel(II) hydrides (1–3) with different alkynes were investigated. Although the first step is the insertion of alkyne into the Ni–H bond for each reaction, different final products were isolated. Normal vinyl nickel complex [2-Ph2P(4-Me-C6H3)S]Ni(CPh═CH2)(PMe3) (4) was obtained by the reaction of phenylacetylene with 1. The nickelacyclopropane complexes [2-Ph2P(6-Me3Si-C6H3)S]Ni[Ph(PMe3)C–CH2] (5), [2-Ph2P(4-Me3Si-C6H3)S]Ni[Ph(PMe3)C–CH2] (6), [2-Ph2P(4-Me3-C6H3)S]Ni[Ph(PMe3)C–CHPh] (7), [2-Ph2P(6-Me3Si-C6H3)S]Ni[Ph(PMe3)C–CHPh] (8), [2-Ph2P(4-Me3Si-C6H3)S]Ni[Ph(PMe3)C–CHPh] (9), [2-Ph2P(4-Me-C6H3)S]Ni[Ph(PMe3)C–CHSiMe3] (10) or [2-Ph2P(4-Me-C6H3)S]Ni[Me3Si(PMe3)C–CHPh] (10), [2-Ph2P(6-Me3Si-C6H3)S]Ni[Ph(PMe3)C–CHSiMe3] (11) or [2-Ph2P(6-Me3Si-C6H3)S]Ni[Me3Si(PMe3)C–CHPh] (11), and [2-Ph2P(4-Me3Si-C6H3)S]Ni[Ph(PMe3)C–CHSiMe3] (12) or [2-Ph2P(4-Me3Si-C6H3)S]Ni[Me3Si(PMe3)C–CHPh] (12) containing a ylidic ligand were formed by the reaction of phenylacetylene, diphenylacetylene, and 1-phenyl-2-(trimethylsilyl)acetylene with 1, 2, and 3, respectively. The phenyl/vinyl exchange nickel(II) complexes [2-(Ph(CH2═CSiMe3)P(4-Me-C6H3)S]Ni(Ph)(PMe3) (13), [2-(Ph(CH2═CSiMe3)P((6-Me3Si-C6H3)S]Ni(Ph)(PMe3) (14), and [2-(Ph(CH2═CSiMe3)P((4-Me3Si-C6H3)S]Ni(Ph)(PMe3) (15) could be obtained by insertion of trimethylsilylacetylene into Ni–H bonds of 1, 2, and 3. To the best of our knowledge, this is a novel reaction type between alkyne and nickel hydride. The results indicate that whether increasing the electronegativity on the benzene ring or on the alkyne leads to the instability of the vinyl nickel complex, and is beneficial to the C–P reductive elimination to form nickelacyclopropane complexes or phenyl nickel complexes via vinyl/phenyl exchange reaction in the case of the more electronegative nickel center. All the nickel complexes were fully detected by IR, NMR and the molecular structures of complexes 1, 2, 7, 9, 13, and 14 were confirmed by single crystal X-ray diffraction.

Synthesis and reactivity of iron hydride with [P, Se]-chelate ligand

Co-reporter:Hongwei Zhou, Huaxin Luan, Tingting Zheng, Xinghao Qi, Hongjian Sun, Xiaoyan Li, Olaf Fuhr, Dieter Fenske

Journal of Organometallic Chemistry 2017 Volume 853(Volume 853) pp:

Publication Date(Web):15 December 2017

DOI:10.1016/j.jorganchem.2017.10.037

•Hydrido iron complex bearing [P, Se]-chelate ligand was prepared.•Reaction of hydrido iron complex with HCl was studied.•Ligand replacement of PMe3 in hydrido iron complex by CO was explored.The synthesis and reactivity of a novel iron hydride supported by [P, Se]-chelate ligand have been explored. Iron hydride o-(Ph2P)C6H4SeFeH(PMe3)3 (1) was obtained via the reaction of (o-PPh2)PhSeH with Fe(PMe3)4. Complex 1 reacted with HCl or acetylacetone delivered a bis-chelated iron complex (o-(Ph2P)C6H4Se)2Fe(PMe3) (2). Through the substitution reaction of PMe3 ligand of complex 1 by CO, monocarbonyl iron(II) hydride o-(Ph2P)C6H4SeFeH(CO) (PMe3)2 (3) with two isomers 3A and 3B was obtained. The molecular structures of complexes 1 and 2 were determined by single crystal X-ray diffraction.

Synthesis of fluorophenyl carbonyl cobalt(I) complexes and decarbonylation of 2,4,5-trifluorobenzaldehyde catalyzed by CoMe(PMe3)4

Co-reporter:Shuo Yuan, Hongjian Sun, Shumiao Zhang, Xiaoyan Li

Inorganica Chimica Acta 2016 Volume 439() pp:100-105

Publication Date(Web):1 January 2016

DOI:10.1016/j.ica.2015.10.006

•C–H activation of aldehyde by cobalt complex.•Decarbonylation of aldehyde was carried out by cobalt complex.•Decarbonylation of 2,4,5-trifluorobenzaldehyde was catalyzed by cobalt complex.•Fluorophenyl carbonyl cobalt complexes were synthesized.Three fluorophenyl carbonyl cobalt(I) complexes PhF(PMe3)3Co(CO) (1–3) were synthesized by the reaction of fluoro-benzaldehydes with CoMe(PMe3)4 via C–H bond activation and decarbonylation reaction. The dicarbonyl cobalt(I) complex (2,4-F2C6H3)Co(CO)2(PMe3)2 (4) was obtained by reacting of complex 1 with CO. Complex 1 reacted with pentafluorobromobenzene afforded cobalt(II) bromide (2,4-F2C6H3)Co(Br)(PMe3)3 (5) with the formation of perfluorinated diphenyl. The reaction of complex 3 and phenylacetylene delivered the hydrido diethinyl cobalt(III) complex (PhCC)2Co(H)(PMe3)3 (6) with 1,2,4-trifluorobenzene as a byproduct. The molecular structures of 1, 4 and 5 were determined by X-ray diffraction. Furthermore, we found that CoMe(PMe3)4 could be used as a catalyst for the catalytic decarbonylation of 2,4,5-trifluorobenzaldehyde with triethylsilane as a hydrogen source.Three fluorophenyl carbonyl cobalt(I) complexes PhF(PMe3)3Co(CO) (1–3) were synthesized by the reaction of fluoro-benzaldehydes with CoMe(PMe3)4 via C–H bond activation and decarbonylation reaction. The chemical properties of complexes 1 and 3 were studied. The catalytic decarbonylation of 2,4,5-trifluoro-benzaldehyde to 1,2,4-trifluorobenzene by CoMe(PMe3)4 was explored. A mechanism of the catalytic decarbonylation reaction was speculated with the support of experiment.

Selective C–F and C–H Activation of Fluoroarenes by Fe(PMe3)4 and Catalytic Performance of Iron Hydride in Hydrosilylation of Carbonyl Compounds

Co-reporter:Tingting Zheng, Junye Li, Shumiao Zhang, Benjing Xue, Hongjian Sun, Xiaoyan Li, Olaf Fuhr, and Dieter Fenske

Organometallics 2016 Volume 35(Issue 20) pp:3538-3545

Publication Date(Web):September 30, 2016

DOI:10.1021/acs.organomet.6b00546

The reactions of perfluorinated toluene (CF3C6F5), pentafluoropyridine (C5NF5), and hexafluorobenzene (C6F6) with the iron(0) complex Fe(PMe3)4 were investigated. The Fe(I) complexes (4-CF3C6F4)Fe(PMe3)4 (1), (4-C5NF4)Fe(PMe3)4 (2), and (C6F5)Fe(PMe3)4 (3) were obtained by selective activation of the C–F bonds. However, under similar reaction conditions, the reaction of Fe(PMe3)4 with perfluoronaphthalene (C10F8) afforded a π-coordinated Fe(0) complex, (η4-1,2,3,4-C10F8)Fe(PMe3)3 (4), and the expected C–F bond activation reaction was not observed. The expected iron hydride (C6F5)FeH(PMe3)4 (6) could be obtained in a yield of 80% by the reaction of bromopentafluorobenzene with Fe(PMe3)4 and subsequent reduction with NaBH4. The molecular structures of complexes 2, 4, and 6 were determined by single-crystal X-ray diffraction. Complexes 1–4 and 6 could be used as catalysts for the hydrosilylation of carbonyl compounds. Among them, complex 6 is the best catalyst. The selective reduction of carbonyl groups of α,β-unsaturated aldehydes and ketones was also realized with 6 as catalyst.

Synthesis of Iron Hydrides by Selective CF/CH Bond Activation in Fluoroarylimines and Their Applications in Catalytic Reduction Reactions

Co-reporter:Lin Wang;Hongjian Sun

European Journal of Inorganic Chemistry 2015 Volume 2015( Issue 16) pp:2732-2743

Publication Date(Web):

DOI:10.1002/ejic.201500313

Abstract

The reactions of Fe(PMe₃)₄ with different 2,6-diflurophenylarylimines 1–5 were explored. Fluoroarylimines 1–3, the aryl rings of which are substituted with electron-withdrawing groups, reacted with Fe(PMe₃)₄ to afford the C–H activation products 6–8. However, if the aryl rings of the fluoroarylimines were substituted with electron-donating groups, the iron hydrides 9 and 10 were obtained from the reactions of the fluoroarylimines with Fe(PMe₃)₄ through C–F bond activation. In a further study, silanes, especially triethoxysilane, were found to benefit the reactions and improve the yields of the hydridoiron complexes. The three-component reaction of Fe(PMe₃)₄, a fluoroarylimine, and a silane could also be utilized in reactions involving 2,6-(CH₃)₂C₆H₃–C(=NH)–2,6-F₂C₆H₃ (13) and 2,6-F₂C₆H₃–C(=NH)–C₆F₅ (16) to synthesize iron hydrides (15 and 18). The hydridoiron complexes could be utilized as efficient catalysts in the hydrosilylation of aldehydes and ketones. Furthermore, cinnamaldehydes were selectively reduced to the corresponding cinnamyl alcohols in high yields. The mechanism of the catalytic reduction reaction was studied extensively through operando IR spectroscopy.

Syntheses and catalytic application of hydrido iron(II) complexes with [P,S]-chelating ligands in hydrosilylation of aldehydes and ketones

Co-reporter:Benjing Xue, Hongjian Sun and Xiaoyan Li

RSC Advances 2015 vol. 5(Issue 64) pp:52000-52006

Publication Date(Web):02 Jun 2015

DOI:10.1039/C5RA09330A

Four hydrido iron(II) complexes (1–4) with [P,S]-chelating ligands were synthesized by the reactions of (2-diphenylphosphanyl)thiophenols, C6H3(1-SH) (2-PPh2) (4-R1) (6-R2), abbreviated as (P^SH), with Fe(PMe3)4. (1: R1 = R2 = H; 2: R1 = H, R2 = SiMe3; 3: R1 = CH3, R2 = H; 4: R1 = SiMe3, R2 = H). Among them, complexes 2–4 are new and were completely characterized by spectroscopic methods. The molecular structures of complexes 2, 3, and 4 were confirmed by X-ray single crystal diffraction. The catalytic properties of hydrido iron(II) complexes 1–4 were explored in the hydrosilylation of aldehydes and ketones. They showed a good activity in catalytic hydrosilylation of aldehydes and ketones by using (EtO)3SiH as a hydrogen source under mild conditions.

Formation of PCP pincer cobalt complexes with cobaltacyclopropane moieties via double Csp3–H bond activation

Co-reporter:Gengyu Zhu, Lin Wang, Hongjian Sun and Xiaoyan Li

RSC Advances 2015 vol. 5(Issue 25) pp:19402-19408

Publication Date(Web):09 Feb 2015

DOI:10.1039/C5RA01230A

The introduction and changes of the substituents at the middle carbon atom of the preligand dipyrrolmethane have a significant impact on the reaction results. When the substituent at the Csp3 atom is a methyl group, the reaction of the preligand with CoMe(PMe3)4 delivered cobalt(I) complex 2 as a Csp3–H bond activation product. In the case of ethyl, propyl and pentyl groups, PCP pincer cobalt complexes 3–5 with cobaltacyclopropane moieties were formed via double Csp3–H bond activation. With iso-propyl as the substituent, cobalt(I) complex 6 as Csp2–H activation product was obtained.

Synthesis of Vinylnickel and Nickelacyclopropane Complexes Containing a Chelate [P,Se]-Ligand

Co-reporter:Hongwei Zhou;Hongjian Sun;Tingting Zheng;Shumiao Zhang

European Journal of Inorganic Chemistry 2015 Volume 2015( Issue 19) pp:3139-3145

Publication Date(Web):

DOI:10.1002/ejic.201500293

Abstract

The reaction of 2-(diphenylphosphanyl)benzeneselenol with Ni(PMe₃)₄ yielded the hydridonickel(II) complex [Ph₂P(C₆H₄)Se]NiH(PMe₃)₂ (1). The insertion reactions of 1 with alkynes have been investigated. The vinylnickel complexes [Ph₂P(C₆H₄)Se]Ni(CPh=CH₂)(PMe₃) (2) and [Ph₂P(C₆H₄)Se]Ni(CCH₃=CHPh)(PMe₃) (3) were obtained by reacting phenylacetylene and 1-phenyl-1-propyne with 1. The nickelacyclopropane complexes [Ph₂P(C₆H₄)Se]Ni[Ph(PMe₃)C–CHPh] (4), [Ph₂P(C₆H₄)Se]Ni[(SiMe₃)(PMe₃)C–CH₂] (5) and 6 (6A and 6B) containing an ylidic ligand were obtained by reacting diphenylacetylene, (trimethylsilyl)acetylene, and 1-phenyl-2-(trimethylsilyl)acetylene with 1. The molecular structures of 1–5 were determined by single-crystal X-ray diffraction.

Synthesis and Reactivity of a Hydrido CNC Pincer Cobalt(III) Complex and Its Application in Hydrosilylation of Aldehydes and Ketones

Co-reporter:Hongwei Zhou, Hongjian Sun, Shumiao Zhang, and Xiaoyan Li

Organometallics 2015 Volume 34(Issue 8) pp:1479-1486

Publication Date(Web):April 15, 2015

DOI:10.1021/om5011929

Reaction of the N-benzylidene-1-naphthylamine with CoMe(PMe3)4 afforded the hydrido CNC pincer cobalt complex CoH(PMe3)2[(C6H4)CH═N(C10H6)] (1) via double C–H bond activation. In the 1H NMR spectrum, a triplet at −18.98 ppm is the typical signal of the hydrido ligand (Co–H). Complex 1 reacted with haloalkane (CH3I and EtBr) to deliver CoX(PMe3)2((C6H4)CH═N(C10H6)) (X = I (2); Br (3)). However, the reactions of complex 1 with HCl and trifluoroacetic acid (TFA) delivered HCoCl(PMe3)2((C6H4)CH═N(C10H7)) (4) and HCo(OCOCF3)(PMe3)2((C6H4)CH═N(C10H7)) (5) with the cleavage of the Co–C(naphthyl) bond. In the 1H NMR spectra, the signals of the hydrido ligands were found at −21.31 (4) and −18.71 (5) ppm. A reaction of complex 1 with DCl was carried out to prove that the hydrogen atom eliminated to the naphthyl carbon comes from HCl. Complex 1 reacted with acetylacetone, resulting in the formation of Co(acac)(PMe3)2((C6H5)CHNH(C10H6)) (7). Complex 1 was found to be an efficient catalyst for hydrosilylation of aldehydes and ketones. The molecular structures of complex 1, 2, 4, and 7 were determined by X-ray single-crystal diffraction.

Imine Nitrogen Bridged Binuclear Nickel Complexes via N–H Bond Activation: Synthesis, Characterization, Unexpected C,N-Coupling Reaction, and Their Catalytic Application in Hydrosilylation of Aldehydes

Co-reporter:Lin Wang, Hongjian Sun, and Xiaoyan Li

Organometallics 2015 Volume 34(Issue 20) pp:5175-5182

Publication Date(Web):October 13, 2015

DOI:10.1021/acs.organomet.5b00734

The reactions of NiMe2(PMe3)3 with 2,6-difluoroarylimines were explored. As a result, a series of binuclear nickel complexes (5–8, 11) were synthesized. Meanwhile, from the reactions of NiMe2(PMe3)3 with [2-CH3C6H4-C(═NH)-2,6-F2C6H3] (9) and [2,6-(CH3)2C6H3-C(═NH)-2,6-F2C6H3] (10), two unexpected C,N-coupling products (12 and 13) were obtained. It is believed that these coupling reactions underwent activation of the N–H and C–F bonds. The binuclear nickel complexes showed excellent catalytic activity in the hydrosilylation of aldehydes. The mechanism of the reaction was studied through stoichiometric reactions, and the double-(η2-Si–H)–NiII intermediate was detected by in situ 1H NMR spectroscopy, which may be the key point in the catalytic cycle.

Selective Alkylation and Arylation of C–F Bond with Grignard Reagents

Co-reporter:Faguan Lu, Hongjian Sun, Aiqin Du, Lei Feng, and Xiaoyan Li

Organic Letters 2014 Volume 16(Issue 3) pp:772-775

Publication Date(Web):January 16, 2014

DOI:10.1021/ol403479r

Selective alkylation and arylation of the C–F bonds of polyfluoroaryl imines with Grignard reagents were discovered in the absence of metal catalysts. The aldazine-N atom as an anchoring group has a special effect on the regioselectivity of the reaction. The C═N bond addition reaction with Grignard reagents was also explored. A possible mechanism was proposed on the competition between the nucleophilic substitution and addition reaction.

Computational rationalization of the selective C–H and C–F activations of fluoroaromatic imines and ketones by cobalt complexes

Co-reporter:Jingjing Li, Dongju Zhang, Hongjian Sun and Xiaoyan Li

Organic & Biomolecular Chemistry 2014 vol. 12(Issue 12) pp:1897-1907

Publication Date(Web):22 Jan 2014

DOI:10.1039/C3OB42384K

While selective C–H and C–F activations of fluoroaromatic imines and ketones with transition metal complexes supported by PMe3 have been successfully achieved in recent publications, insight into the molecular mechanism and energetics of those reactions is still lacking. Focusing on three typical substrates, 2,6-difluorobenzophenone imine (A) and 2,6-difluorobenzophenone (B), and 2,4′-difluorobenzophenone (C), the present work theoretically studied their C–H and C–F cyclometalation reactions promoted by the activator Co(PMe3)4 or CoMe(PMe3)4. It is found that reaction A + Co(PMe3)4 favors the C–F activation, reaction A + CoMe(PMe3)4 prefers the C–H activation, whereas both the C–H and C–F activation pathways may be viable for reactions B + CoMe(PMe3)4 and C + CoMe(PMe3)4. The experimentally observed C–H and C–F cyclometalation products have been rationalized by analyzing the thermodynamic and kinetic properties of two activation pathways. From calculated results combined with the experimental observations, we believe that three factors, i.e. the oxidation state of the metal center in the activators, the anchoring group of substrates, and substituted fluoroatom counts of the aromatic ring in substrates, affect the selectivity of C–H and C–F activations of fluoroaromatic ketones and imines. Calculated results are enlightening about the rational design of activators and substrates of fluoroaromatic imines and ketones to obtain the exclusive C–H or C–F bond activation product.

Reactivity of mer-hydrido(2-mercaptobenzoyl)tris(trimethylphosphine)cobalt(III) complex

Co-reporter:Qingfen Niu, Hongjian Sun, Lin Wang, Qingping Hu and Xiaoyan Li

Dalton Transactions 2014 vol. 43(Issue 10) pp:4059-4066

Publication Date(Web):28 Nov 2013

DOI:10.1039/C3DT52519H

The reactivity of mer-hydrido(2-mercaptobenzoyl)tris(trimethylphosphine)cobalt(III) complex 1 was intensively studied. A series of sulfur-coordinated organocobalt complexes (2–8) were obtained through the reactions of 1 with RX (RX = HCl, C2H5Br and CH3I), 2-(diphenylphosphanyl)phenol, 2-(diphenylphosphino)benzenethiol, and CO. The reaction of complex 1 with ethynyltrimethylsilane under 1 bar of CO afforded a penta-coordinate cobalt(I) complex 11via insertion reaction of CC bond of ethynyltrimethylsilane into Co–H bond and subsequent C,C-coupling reaction (reductive elimination). The formation mechanism of 11 was proposed and partly-experimentally verified. As an intermediate, the tetra-coordinate cobalt(I) complex 13 was isolated through the reaction of complex 1 with ethynyltrimethylsilane in the absence of CO. The crystal structures of complexes 2–4, 8 and 11 were determined by X-ray diffraction.

Hydrosilylation of aldehydes and ketones catalyzed by hydrido iron complexes bearing imine ligands

Co-reporter:Zhenyu Zuo, Hongjian Sun, Lin Wang and Xiaoyan Li

Dalton Transactions 2014 vol. 43(Issue 30) pp:11716-11722

Publication Date(Web):03 Jun 2014

DOI:10.1039/C4DT00944D

Two new hydrido iron complexes (2 and 4) were synthesized by the reactions of (4-methoxyphenyl)phenylketimine ((4-MeOPh)PhCNH) with Fe(PMe3)4 or FeMe2(PMe3)4. The molecular structures of complexes 2 and 4 were confirmed by X-ray single crystal diffraction. Using hydrido iron complexes (1–4) as catalysts, the hydrosilylations of aldehydes and ketones were investigated. The four complexes were effective catalysts for this reduction reaction. Complex 1 among them is the best catalyst.

Preparation of organocobalt complexes through C–F/C–H bond activation of polyfluoroaryl imines

Co-reporter:Faguan Lu, Hongjian Sun, Lin Wang, Xiaoyan Li

Inorganic Chemistry Communications 2014 Volume 43() pp:110-113

Publication Date(Web):May 2014

DOI:10.1016/j.inoche.2014.02.017

•Synthesis and characterization of organocobalt complex•C–F/C–H bond activation•Cobalt complex supported by trimethylphosphine ligands•C,C-coupling reactionIn this paper, we reported the CF and CH bond activation of polyfluoroimine ligands induced by CoMe(PMe3)4. The reaction of pentafluorophenylmethylidene-2,6-diisopropylaniline 1 with CoMe(PMe3)4 afforded an ortho-chelated cobalt(I) complex [Co(PMe3)3(C6F4-ortho-CH = N-C6H3(iso-Pr)2(ortho, ortho))] (5) via CF bond activation and subsequent elimination of methyl fluoride. Under similar reaction conditions, the reactions of polyfluoroaryl imines 2–4 with CoMe(PMe3)4 afforded the penta-coordinate cobalt(I) complexes 6–8 via CH bond activation and subsequent elimination of methane [Co(PMe3)3(C6H2F2(meta, meta)-ortho-(CH = N-C6H4Clpara)] (6), [Co(PMe3)3(C6H2F2(meta, para)-ortho-(CH = N-C6H4Clpara)] (7), and [Co(PMe3)3(C6HF3(meta, meta, para)-ortho-(CH = N-C6H4Clpara)] (8). Complexes 5–8 were characterized through IR, 1H NMR, 31P NMR, 19F NMR and elemental analyses. The crystal and molecular structures of complexes 5, 6 and 8 were determined by X-ray single crystal diffraction. The reactions of 8 with MeI and EtBr afforded organic fluorides 9–10. A proposed formation mechanism of 9–10 with the oxidative addition of RX at the cobalt(I) center of 8 and reductive elimination via C,C-coupling was discussed.Four organocobalt(I) complexes were prepared by reactions of polyfluorinated imines with CoMe(PMe3)4 via CF or CH activation with imine as an anchoring group. Demetallation of these organocobalt(I) complexes by MeI and EtBr afforded organic fluorides via C,C-coupling. The molecular structures of three organocobalt(I) complexes were determined by X-ray diffraction.

Selective C–H bond activation of 1,2,4,5-tetrafluorobenzene by Co(PMe3)4

Co-reporter:Faguan Lu, Junye Li, Hongjian Sun, Xiaoyan Li

Inorganica Chimica Acta 2014 Volume 416() pp:222-225

Publication Date(Web):24 May 2014

DOI:10.1016/j.ica.2014.03.025

•Selective C–H bond activation of 1,2,4,5-tetrafluorobenzene by Co(PMe3)4.•C–F bond activation and functionalization of polyfluoro organic compounds with transition metal complexes.•C–H/C–F bond competitive reactions by cobalt(0) complex, Co(PMe3)4.Co(I) complex (p-C6F4H)Co(PMe3)3 (1) was obtained by the selective activation of the C–H bond of 1,2,4,5-tetrafluorobenzene (C6F4H2) with cobalt(0) complex, Co(PMe3)4. At the same time, 1,2,4-trifluorobenzene was observed as the hydrodefluorination product. The reaction of C6F4H2 with Co(PMe3)4 under 1 bar of CO at room temperature afforded dicarbonyl cobalt(I) complex (p-C6F4H)Co(CO)2(PMe3)2 (2). Treatment of the mixtures of C6F4H2/Co(PMe3)4 with hexachlorobenzene resulted in stable cobalt(II) chloride (p-C6F4H)CoCl(PMe3)3 (3) via C–H bond cleavage with the hydrodechlorination products pentachlorobenzene (C6Cl5H) and 1,2,4,5-tetrachlorobenzene C6Cl4H2. The structures of complexes 2 and 3 were determined by X-ray single crystal diffraction.In this paper we reported the selective C–H bond activation of 1,2,4,5-tetrafluorobenzene by Co(PMe3)4. Three cobalt complexes, (p-C6F4H)Co(PMe3)3 (1), (p-C6F4H)Co(CO)2(PMe3)2 (2) and (p-C6F4H)CoCl(PMe3)3 (3) were obtained. The structures of complexes 2 and 3 were determined by X-ray single crystal diffraction.

Synthesis and Catalytic Property of Iron Pincer Complexes Generated by Csp3–H Activation

Co-reporter:Hua Zhao, Hongjian Sun, and Xiaoyan Li

Organometallics 2014 Volume 33(Issue 13) pp:3535-3539

Publication Date(Web):July 1, 2014

DOI:10.1021/om500429r

When the diphosphinito PCP ligand (Ph2P(C6H4))2CH2 (1) was treated with Fe(PMe3)4 and FeMe2(PMe3)4, the Csp3–H activation products [(Ph2P(C6H4))2CH]Fe(H)(PMe3)2 (2) and [(Ph2P(C6H4))(PhP(C6H4)2)CH]Fe(PMe3)2 (3) were obtained at room temperature. The generation of product 3 underwent one Csp3–H and one Csp2–H bond activation process. The new iron hydride complex 2 showed good activity in the catalytic hydrosilylation of aldehydes and ketones by using (EtO)3SiH as the hydrogen source under mild conditions. Complexes 2 and 3 were characterized by spectroscopic methods and X-ray diffraction analysis.

Transition-Metal-Free Synthesis of Fluorinated Arenes from Perfluorinated Arenes Coupled with Grignard Reagents

Co-reporter:Yunqiang Sun, Hongjian Sun, Jiong Jia, Aiqin Du, and Xiaoyan Li

Organometallics 2014 Volume 33(Issue 4) pp:1079-1081

Publication Date(Web):February 11, 2014

DOI:10.1021/om4011609

A simple method to obtain organofluorine compounds from perfluorinated arenes coupled with Grignard reagents in the absence of a transition-metal catalyst was reported. In particular, the perfluorinated arenes could react not only with aryl Grignard reagents but also with alkyl Grignard reagents in moderate to good yields.

Synthesis, photophysical and thin-film self-assembly properties of novel fluorescent molecules with carbon–carbon triple bonds

Co-reporter:Qingfen Niu, Hongjian Sun, Xiaoyan Li

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2014 Volume 133() pp:229-240

Publication Date(Web):10 December 2014

DOI:10.1016/j.saa.2014.05.063

•Three novel fluorescent molecules with carbon–carbon triple bonds 2TBEA, 2TBDA and TEPEB were designed and synthesized.•Their optical and electrochemical properties were investigated.•Thin-film materials.Three novel fluorescent molecules with carbon–carbon triple bonds 2TBEA, 2TBDA and TEPEB are successfully designed and synthesized. Their thermal, photophysical, electrochemical, electronic and thin-film self-assembly properties were characterized. Three dyes showed typical photoluminescence (PL) emission behaviors, the PL intensities firstly increased and then decreased with gradually decreasing concentration. The appealing fluorescence properties indicated that three dyes could be used as good fluorescent materials. Additionally, the thin-film self-assembly behaviors of three dyes were also investigated. The microstructures of their optical microscopy (OM) images exhibited high flexibility. Furthermore, SEM and AFM surface morphology of these self-assembly nanostructures revealed that three well-defined long-range order of rod-like and tube-like self-assembly systems exhibited interesting morphology properties. Therefore, three compounds may be of great interest for the development of organic thin-film materials.Graphical abstract

Selective activation of C–F and C–H bonds with iron complexes, the relevant mechanism study by DFT calculations and study on the chemical properties of hydrido iron complex

Co-reporter:Xiaofeng Xu, Jiong Jia, Hongjian Sun, Yuxia Liu, Wengang Xu, Yujie Shi, Dongju Zhang and Xiaoyan Li

Dalton Transactions 2013 vol. 42(Issue 10) pp:3417-3428

Publication Date(Web):20 Nov 2012

DOI:10.1039/C2DT31795H

The reactions of (2,6-difluorophenyl)phenylmethanone (2,6-F2C6H3–C(O)–C6H5) (1) and (2,6-difluorophenyl)phenylmethanimine (2,6-F2C6H3–C(NH)–C6H5) (3) with Fe(PMe3)4 afforded different selective C–F/C–H bond activation products. The reaction of 1 with Fe(PMe3)4 gave rise to bis-chelate iron(II) complex [C6H5–C(O)–3-FC6H3)Fe(PMe3)]2 (2) via C–F bond activation. The reaction of 3 with Fe(PMe3)4 delivered chelate hydrido iron(II) complex 2,6-F2C6H3–C(NH)–C6H4)Fe(H)(PMe3)3 (4) through C–H bond activation. The DFT calculations show the detailed elementary steps of the mechanism of formation of hydrido complex 4 and indicate 4 is the kinetically preferred product. Complex 4 reacted with HCl, CH3Br and CH3I delivered the chelate iron halides (2,6-F2C6H3–C(NH)–C6H4)Fe(PMe3)3X (X = Cl (5); Br (6); I (7)). A ligand (PMe3) replacement by CO of 4 was observed giving (2,6-F2C6H3–C(NH)–C6H4)Fe(H)(CO)(PMe3)2 (8). The chelate ligand exchange occurred through the reaction of 4 with salicylaldehydes. The reaction of 4 with Me3SiCCH afforded (2,6-F2C6H3–C(N)–C6H5)Fe(CC–SiMe3)(PMe3)3 (11). A reaction mechanism from 4 to 11 was discussed with the support of IR monitoring. The molecular structures of complexes 2, 4, 6, 7, 10 and 11 were determined by X-ray diffraction.

Selectively catalytic hydrodefluorination of perfluoroarenes by Co(PMe3)4 with sodium formate as reducing agent and mechanism study

Co-reporter:Junye Li, Tingting Zheng, Hongjian Sun and Xiaoyan Li

Dalton Transactions 2013 vol. 42(Issue 36) pp:13048-13053

Publication Date(Web):19 Jun 2013

DOI:10.1039/C3DT50409C

Successful selective hydrodefluorinations of aryl fluorides were carried out in the presence of a cobalt catalyst supported by trimethylphosphine and with sodium formate as a reducing agent in acetonitrile or DMSO. Octafluorotoluene (1), pentafluoropyridine (2), hexafluorobenzene (3), pentafluorobenzene (3a) and perfluorobiphenyl (4) were studied to investigate the scope of this catalytic system. It was found that the fluorinated compounds 1, 2 and 4 with electron-withdrawing groups are more active than 3 and 3a. The catalytic hydrodefluorination mechanism is proposed and discussed with the support of the experimental results of the stoichiometric reactions and the in situ IR and NMR data.

Novel phenyl-oligothiophene derivatives containing acetylenic spacers for thin film materials: Synthesis, photophysical and morphology properties

Co-reporter:Qingfen Niu, Yunqiang Lu, Hongjian Sun, Xiaoyan Li, Xutang Tao

Dyes and Pigments 2013 Volume 97(Issue 1) pp:184-197

Publication Date(Web):April 2013

DOI:10.1016/j.dyepig.2012.12.012

Four novel organic semiconductor phenyl-oligothiophene derivatives containing acetylenic spacers, 5-(phenylethynyl)-2,2′:5′,2″-terthiophene, 5-(phenylethynyl)-2,2′:5′,2″:5″,2‴-quaterthiophene, 4-([2,2′:5′,2″-terthiophen]-5-ylethynyl)aniline, 4-((5′-iodo-[2,2′-bithiophen]-5-yl)ethynyl)aniline were synthesized and studied with respect to their thermal, photophysical, electrochemical and morphological properties. TGA and DSC results show all the oligomers have good thermal stability. Electrochemical measurements suggest the compounds can be used as photovoltaic materials. UV–vis spectra confirm all the molecules adopt close side-to-side packing, indicating H-aggregation. 4-([2,2′:5′,2″-Terthiophen]-5-ylethynyl)aniline exhibits excellent fluorescence properties when applied in an optoelectric field. XRD analysis indicates that the four compounds have a high degree of lamellar ordering and crystallinity. Film morphology properties reveal a clearly single-crystalline monoclinic morphology with lamellae parallel to the substrate, exhibiting that adjacent molecules have a strong intermolecular interaction. The potential liquid crystalline property is illustrated by DSC, XRD and polarization optical microscopy. These properties demonstrate that these oligomers could be promising candidates for the organic thin film materials and photovoltaic devices.Highlights► Four novel materials PE3T, PE4T, 3TEA, I2TEA were successfully synthesized. ► The thermal, optical, electrochemical and morphological properties were studied. ► Four molecules adopted H aggregation and exhibited high film performance. ► All the oligomers were promising candidates for the organic thin film materials.

Selective C–F/C–H bond activation of fluoroarenes by cobalt complex supported with phosphine ligands

Co-reporter:Junye Li, Tingting Zheng, Hongjian Sun, Wengang Xu and Xiaoyan Li

Dalton Transactions 2013 vol. 42(Issue 16) pp:5740-5748

Publication Date(Web):28 Jan 2013

DOI:10.1039/C3DT33074E

The reactions of pentafluoropyridine C5NF5, hexafluorobenzene C6F6, and perfluoronaphthalene C10F8 with cobalt(0) complex, Co(PMe3)4, were investigated. The Co(I) complexes (4-C5NF4)Co(PMe3)3 (1), (C6F5)Co(PMe3)3 (2), (C10F7)Co(PMe3)3 (3), (4-C5NF4)Co(PMe3)4 (4) and (C10F7)Co(PMe3)4 (6) were obtained by selective activation of the C–F bonds. The reactions of 1 and 2 with CO afforded dicarbonyl cobalt(I) complexes (4-C5NF4)Co(CO)2(PMe3)2 (7), (C6F5)Co(CO)2(PMe3)2 (8). Under similar reaction conditions, 2 as a C–H bond activation product was obtained from the reaction of pentafluorobenzene, C6F5H, with Co(PMe3)4. The byproducts, hydrodefluorination product 1,2,4,5-C6F4H2 and F2PMe3 from the reaction of C6F5H and Co(PMe3)4 were also observed. The reaction mechanism of C6F5H with Co(PMe3)4 is proposed and partly-experimentally verified. The reaction of C6F5H with Co(PMe3)4 under 1 bar of CO at room temperature afforded hydrido dicarbonyl cobalt(II) complex (C6F5)Co(H)(CO)2(PMe3)2 (11). Treatment of the mixtures of C6F5H/Co(PMe3)4 with hexachlorobenzene, C6Cl6, resulted in (C6F5)CoCl(PMe3)3 (12) via C–H bond cleavage with the hydrodechlorination product pentachlorobenzene, C6Cl5H, and 1,2,4,5-tetrachlorobenzene, C6Cl4H2. The structures of complexes 1, 2, 6, 7, 8, 11 and 12 were determined by X-ray diffraction.

Cobalt-catalyzed Selective CF Bond Activation and Alkylation of Polyfluoroaryl Imines

Co-reporter:Faguan Lu;Hongjian Sun

Chinese Journal of Chemistry 2013 Volume 31( Issue 7) pp:927-932

Publication Date(Web):

DOI:10.1002/cjoc.201300340

Abstract

In this paper the CF bond activation of polyfluoroaryl imines is explored at cobalt(0) center with an imine-N atom as an anchoring group. The reaction of F₅C₆-CHN-(2′-ClC₆H₄) (2) and F₅C₆-CHN-C₆H₅ (3) with Co(PMe₃)₄ afforded the CF bond activation products (ortho-F₄C₆-CHN-(2′-ClC₆H₄))Co(I)(PMe₃)₃ (5) and (ortho-F₄C₆-CHN-C₆H₅)Co(II)(F)(PMe₃)₂ (6), while only π-(CN) coordinated cobalt(0) complex (2,4,5-F₃C₆H₂-CHN-(4′-ClC₆H₄))Co(0)(PMe₃)₃ (4) was obtained from 2,4,5-F₃C₆H₂-CHN-(4′-ClC₆H₄) (1) without CF bond activation. Complexes 4–6 were characterized through X-ray single crystal diffraction. It was also found that dialkylation of N-(perfluorobenzylidene)benzenamine with organozinc reagents could be catalyzed by Co(PMe₃)₄ via C,C-coupling reaction under mild conditions.

Simple synthesis and structure characterization of a phosphoniomethylidyne tantalum(V) complex

Co-reporter:Nazhen Liu, Gengyu Zhu, Hongjian Sun, Xiaoyan Li

Inorganic Chemistry Communications 2013 Volume 27() pp:36-39

Publication Date(Web):January 2013

DOI:10.1016/j.inoche.2012.10.017

A high-valent phosphoniomethylidyne tantalum complex [(C5Me4H)Ta(C-PPh3)(CH-PPh3)Cl] (3) was obtained via transylidation reactions of (C5Me4H)TaCl4 with 5 equivalents of the phosphorus ylide Ph3P = CH2. The addition of strong base Li(N(SiMe3)2 is beneficial to the transylidation reaction and improves the yield of complex 3. The ylide adduct complex [(C5Me4H)TaCl4(CH2PPh3)] (4) as the reaction intermediate was isolated through the reaction of (C5Me4H)TaCl4 with one equivalent of the phosphorus ylide Ph3P = CH2. Both complexes 3 and 4 were structurally characterized by X-ray single crystal diffraction. A comparison on the preparation and properties of the phosphoniomethylidyne tantalum complexes with different supporting ligands, [CpTa(C-PPh3)(CH-PPh3)Cl] (1) (Cp = cyclopentadieneyl ligand), [(C5Me4H)Ta(C-PPh3)(CH-PPh3)Cl] (3) (C5Me4H = tetramethylcyclopentadienyl ligand) (3) and [Cp⁎Ta(C-PPh3)(CH-PPh3)Cl] (2) (Cp⁎ = pentamethylcyclopentadienyl ligand) was discussed.A high-valent tantalum(V) phosphoniomethylidyne complex [(C5Me4H)Ta(C-PPh3)(CH-PPh3)Cl] (3) was obtained via transylidation reactions of (C5Me4H)TaCl4 with 5 equiv of the phosphorus ylide Ph3P = CH2. With the addition of 3 equiv of LiN(SiMe3)2 and 3 equiv of Ph3P = CH2 complex 3 could be quantitatively obtained within 12 h.Highlights► Synthesis and characterization of a tantalum(V) phosphoniomethylidyne complex. ► Transylidation reactions. ► Tantalum(V) ylide adduct complex. ► Tantalum(V) complex with tetramethylcyclopentadienyl ligand.

Novel planar and star-shaped molecules: Synthesis, electrochemical and photophysical properties

Co-reporter:Qingfen Niu, Yunqiang Lu, Hongjian Sun, Xiaoyan Li

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2013 Volume 107() pp:377-385

Publication Date(Web):15 April 2013

DOI:10.1016/j.saa.2013.01.047

Three novel planar and star-shaped molecules containing thiophene-functionalized group and acetylenic spacers, 4-((5″-iodo-[2,2′:5′,2″-terthiophen]-5-yl)ethynyl)aniline (I3TEA), 4,4′-([2,2′:5′,2″-terthiophene]-5,5″-diylbis(ethyne-2,1-diyl))dianiline (3TDDA), 1,3,5-tris((5-((trimethylsilyl)ethynyl)thiophen-2-yl)ethynyl)benzene (TETEB) were synthesized through Sonogashira coupling reaction. Their photophysical and electrochemical properties were explored by UV–vis, photoluminescence (PL) emission and DFT calculation. Three compounds possess unusual phenomena of PL, with the concentration of gradually decreased, the intensity of PL firstly increased and then decreased, this may be due to the aggregate-enhanced emission (AEE) effect and aggregation-caused quenching (ACQ) effect. Their spectroscopic data demonstrate that D–π–A–π–D structured organic dye 3TDDA based on NH2 as donor units and 3T as acceptor units with acetylenic spacers π-conjugated chain between them exhibits good luminescent properties. Dye I3TEA with donor(D)–acceptor(A) structure shows good charge transfer because of amino functional group and iodine atom. Octupolar organic π-conjugated star-shaped molecule TETEB possesses excellent luminescent properties because of its unique structure applied in the optoelectronic field. The redox curves and results of DFT calculations suggest that three compounds have low ionization potential and low Eoxd. All the good properties demonstrate three compounds could be promising candidates for photovoltaic materials.Graphical abstractHighlights► Three novel materials I3TEA, 3TDDA and TETEB were successfully synthesized. ► Their optical and electrochemical properties were investigated. ► The compounds were promising candidates for photovoltaic materials.

Acid-Promoted Selective Carbon–Fluorine Bond Activation and Functionalization of Hexafluoropropene by Nickel Complexes Supported with Phosphine Ligands

Co-reporter:Wengang Xu, Hongjian Sun, Zichang Xiong, and Xiaoyan Li

Organometallics 2013 Volume 32(Issue 23) pp:7122-7132

Publication Date(Web):November 18, 2013

DOI:10.1021/om400782v

The electron-rich complex Ni(PMe3)4 was utilized to react with perfluoropropene to obtain Ni(CF2═CFCF3)(PMe3)3 (1). The selective C–F bond activation process of the π-coordinated perfluoropropene in 1 was conducted with the promotion of Lewis acids (ZnCl2, LiBr, and LiI) under mild conditions to afford the products Ni(CF3C═CF2)(PMe3)2X (X = Cl (2), Br (3), I (4)). The structures of complexes 2 and 3 determined by X-ray single-crystal diffraction confirmed that the C–F bond activation occurred at the geminal position of the trifluoromethyl group. Surprisingly, CF3COOH as a protonic acid could also carry out a similar activation reaction to give rise to Ni(CF3C═CF2)(CF3COO)(PMe3)2 (7), while only the addition products Ni(CF2CFHCF3)(CH3COO)(PMe3) (5) and Ni(CF2CFHCF3)(CH3SO3)(PMe3) (6) were obtained with CH3COOH and CH3SO3H. The transmetalation products Ni(CF3C═CF2)Ph(PMe3)2 (8), Ni(CF3C═CF2)(p-MeOPh)(PMe3)2 (9), and Ni(CF3C═CF2)(C≡CPh)(PMe3)2 (10) were obtained through the reactions of Ni(CF3C═CF2)(PMe3)2Cl (2) with PhMgBr, (p-MeOPh)MgBr, and PhC≡CLi. In contrast, the reaction of complex 2 with PhCH2CH2MgBr delivered complex 11, Ni(CF3CH═C–CH2CH2Ph)(PMe3)2, via double C–F bond activation. All of the C(sp2)–F bonds in complex 11 were activated and cleaved. The structures of complexes 5 and 7–11 were determined by X-ray single-crystal structure analysis. A reasonable mechanism was proposed and partially experimentally verified through operando IR and in situ 1H NMR spectroscopy.

Nickel-catalyzed C–F bond activation and alkylation of polyfluoroaryl imines

Co-reporter:Xiuxiu Yang, Hongjian Sun, Shumiao Zhang, Xiaoyan Li

Journal of Organometallic Chemistry 2013 723() pp: 36-42

Publication Date(Web):

DOI:10.1016/j.jorganchem.2012.10.013

N–H bond activation of 2-aminobenzophenone by trimethylphosphine complexes of nickel and cobalt

Co-reporter:Zehua Zhang, Hongjian Sun, Wengang Xu, Xiaoyan Li

Polyhedron 2013 50(1) pp: 571-575

Publication Date(Web):

DOI:10.1016/j.poly.2012.12.005

Synthesis and Catalytic Application in Hydrosilylation of the Complex mer-Hydrido(2-mercaptobenzoyl)tris(trimethylphosphine)cobalt(III)

Co-reporter:Qingfen Niu, Hongjian Sun, Xiaoyan Li, H.-F. Klein, and Ulrich Flörke

Organometallics 2013 Volume 32(Issue 18) pp:5235-5238

Publication Date(Web):September 11, 2013

DOI:10.1021/om4005687

The sulfur-coordinated acyl(hydrido)cobalt(III) complex 1 was synthesized by reaction of thiosalicylaldehyde with CoMe(PMe3)4. The crystal structure of 1 was determined by X-ray diffraction. Complex 1 is an excellent catalyst for the hydrosilylation of aldehydes and ketones under mild conditions. This might be the first example of hydrosilylation of aldehydes and ketones catalyzed by (hydrido)cobalt complexes.

Synthesis of 2-Mercaptobenzaldehyde, 2-Mercaptocyclohex-1-enecarboxaldehydes and 3-Mercaptoacrylaldehydes

Co-reporter:Qingfen Niu;Xiaofeng Xu;Hongjian Sun

Chinese Journal of Chemistry 2012 Volume 30( Issue 10) pp:2495-2500

Publication Date(Web):

DOI:10.1002/cjoc.201200433

Abstract

A novel one-pot approach for the preparation of 2-mercaptobenzaldehyde, 2-mercaptocyclohex-1-enecarboxaldehydes and 3-mercaptoacrylaldehydes [(Z)-3-mercapto-2-methyl-3-phenylacrylaldehyde, 3-mercapto-3-(o-tolyl)acrylaldehyde)] starting from ortho-bromobenzaldehyde, 2-chlorocyclohex-1-enecarbaldehydes, (Z)-3-chloro-2-methyl-3-phenylacrylaldehyde and 3-chloro-3-(o-tolyl)acrylaldehyde is reported. The reaction of sulfur with the Grignard reagent of the acetal for the protection of the aldehyde group affords the title compounds through hydrolysis with dilute hydrochloric acid in high yields.

Effect of End-capping Functional Groups on the Optoelectronic Properties of Oligothiophene Derivatives

Co-reporter:Zhenyu Zuo;HongjianPP Sun

Chinese Journal of Chemistry 2012 Volume 30( Issue 10) pp:2401-2410

Publication Date(Web):

DOI:10.1002/cjoc.201200487

Abstract

Five novel oligothiophene derivatives end-capped by different functional groups (R=ethoxyl (EtOP3T), methylsulfanyl (MSP3T), acetyl (AcP3T), methylsulfonyl (MSO₂P3T) and biphenyl (BP3T) groups) were synthesized. They were characterized by Hnuclear magnetic resonanceH (P¹PH NMR), Hmass spectrometryH (MS) and Fourier transform Infra-red spectra (IR). The relationship between end-capping functional groups and optoelectronic properties of them was investigated. It was found that the compound with sulfonyl group in the molecular structure (MSOR₂RP3T) shows the highest oxidation stability (also supported by theoretical calculations) and best thermal stability among the five compounds. The results of scanning electron microscope (SEM) interpret that MSOR₂RP3T displays excellent ability of self-film forming. This reveals that it could be a potential candidate for thin film material. The liquid crystal property of MSOR₂RP3T was characterized by polarized optical microscopy analysis (POM) and X-ray diffraction (XRD). The results of this paper provide useful information for the design of tailored oligothiophene derivatives for devices.

Imine-assisted C–F bond activation by electron-rich iron complexes supported by trimethylphosphine

Co-reporter:Xiaofeng Xu, Hongjian Sun, Yujie Shi, Jiong Jia and Xiaoyan Li

Dalton Transactions 2011 vol. 40(Issue 31) pp:7866-7872

Publication Date(Web):07 Jul 2011

DOI:10.1039/C1DT10843C

C–F bond activation of ortho-fluorinated benzalimines 2,6-F2C6R1R2R3–CHN–R (1–3) using the electron-rich complex Fe(PMe3)4 is reported. With the assistance of the imine group as the anchoring group, bis-chelated iron(II) complexes (C6FR1R2R3–CHN–R)2Fe(PMe3)2 (4–6) were formed. The reaction of 2,6-difluorobenzylidenenaphthalen-1-amine 2,6-F2C6H3–CHN–C10H7 (9) with Fe(PMe3)4 affords [CNC]-pincer iron(II) complex (C6H3F–CHN–C10H6)Fe(PMe3)3 (10) through both C–F and C–H bond activation and π-(CN) coordinate iron(0) complex (C6H3F–CHN–C10H7)2Fe(PMe3)2 (11) with C,C-coupling, while a similar reaction with perfluorobenzylidenenaphthalen-1-amine C6F5–CHN–C10H7 (14) gave rise to only [CNC]-pincer iron(II) complex (C6F4–CHN–C10H6)Fe(PMe3)3 (15). The proposed formation mechanisms of these complexes are discussed. The structures of complexes 5, 6, 10 and 11 were confirmed by X-ray single crystal diffraction.

Carbonylative formation of N-acetyl-2,6-difluorobenzamide through N–H bond activation of 2,6-difluorobenzamide with Ni(II) complex supported with phosphine ligands

Co-reporter:Chenggen Wang, Hongjian Sun, Qingping Hu, Xiaoyan Li

Journal of Organometallic Chemistry 2011 696(15–16) pp: 2815-2819

Publication Date(Web):

DOI:10.1016/j.jorganchem.2011.04.035

Imine-assisted C–F bond activation using low-valent cobalt compounds supported by trimethylphosphine ligands and formation of novel organic fluorides

Co-reporter:Zhe Lian, Xiaofeng Xu, Hongjian Sun, Yue Chen, Tingting Zheng and Xiaoyan Li

Dalton Transactions 2010 vol. 39(Issue 40) pp:9523-9529

Publication Date(Web):31 Aug 2010

DOI:10.1039/C0DT00526F

A cyclometalation reaction involving C–F bond activation at a cobalt(I) center with an aldazine-N atom as anchoring group affords ortho-chelated cobalt(III) complexes containing a [C–Co–F] fragment [CoFMe(PMe3)2{(C6H3F-ortho)CHN–R}] 5–8. Under similar reaction conditions π-coordinated cobalt(0) complexes [Co(PMe3)3((C6H3F-ortho)CHN–R)] 12–14 were formed when [Co(PMe3)4], instead of [CoMe(PMe3)4], was applied. C–F bond activation did not occur. Carbonylation of complexes 6–8 delivered novel organic fluorides 15–17. A proposed formation mechanism of the novel organic fluorides with demetallation and carbonylation of complexes 6–8 by CO is discussed with experimental support. As important intermediates, an acetyl cobalt complex, [CoFMeCO(PMe3)2{(C6H3F-ortho)CHN–R}] 20, and a 19-electron cobalt(0) complex, Co(CO)3(PMe3)221, were structurally characterized. The crystal and molecular structures of complexes 5, 6, 8, 12, 20 and 21 were determined by X-ray diffraction.

Effect of anchoring group and valent of cobalt center on the competitive cleavage of C–F or C–H bond activation

Co-reporter:Tingting Zheng, Hongjian Sun, Jun Ding, Yanfeng Zhang, Xiaoyan Li

Journal of Organometallic Chemistry 2010 695(15–16) pp: 1873-1877

Publication Date(Web):

DOI:10.1016/j.jorganchem.2010.04.031

Synthesis of new thiophenolato hydrido iron(II) complexes and their substitution reactions with alkynes

Co-reporter:Tingting Zheng, Min Li, Hongjian Sun, Klaus Harms, Xiaoyan Li

Polyhedron 2009 28(17) pp: 3823-3827

Publication Date(Web):

DOI:10.1016/j.poly.2009.08.005

Simple Synthesis of (Triphenylphosphoniomethylidene)(pentamethylcyclopentadienyl)titanium(II) Dichloride and Its Unexpected Reduction To Form a Trinuclear Titanium Cluster

Co-reporter:Aichen Wang, Hongjian Sun and Xiaoyan Li

Organometallics 2009 Volume 28(Issue 17) pp:5285-5288

Publication Date(Web):August 11, 2009

DOI:10.1021/om9005406

The novel titanium phosphoniomethylidene complex [Cp*TiCl2(−CH═PPh3)] (2; Cp* = η-C5Me5) was obtained via a transylidation reaction of Cp*TiCl3 (1) with 2 equiv of the phosphorus ylide Ph3P═CH2. The trinuclear titanium(III) cluster [Cp*Ti(μ-Cl)Cl]3 (3) was formed through reduction of complex 2 with CO. Complexes 2 and 3 were structurally characterized by X-ray diffraction.

Synergistic Effect of a Low-Valent Cobalt Complex and a Trimethylphosphine Ligand on Selective C−F Bond Activation of Perfluorinated Toluene

Co-reporter:Tingting Zheng, Hongjian Sun, Yue Chen, Xiaoyan Li, Simon Dürr, Udo Radius and Klaus Harms

Organometallics 2009 Volume 28(Issue 19) pp:5771-5776

Publication Date(Web):September 9, 2009

DOI:10.1021/om900589z

The aryne cobalt complex [Co(4-CF3-η2-C6F3)(PMe3)3] (1) was formed from the reaction of [Co(PMe3)4] and perfluorinated toluene through selective activation of two C−F bonds of perfluorotoluene. A mechanism for the formation of complex 1 is proposed and in most parts experimentally verified. Following this mechanism, a synergistic effect of an electron-rich cobalt(0) center and one of its trimethylphosphine ligands is responsible for the C−F activation of two carbon−fluorine bonds of perfluorotoluene. The detection of difluorotrimethylphoshphorane as the sole byproduct provides strong evidence for this mechanism. Complex [Co(4-CF3-C6F4)(PMe3)3] (4), an intermediate of the proposed mechanism to the aryne complex, was also isolated and structurally characterized. Complex 4 transforms to complex 1 via activation of a second C−F bond of a perfluorotolyl ligand only in the presence of trimethylphosphine in the reaction mixture. Complex 4 reacts with CO under atmospheric pressure and room temperature to give [Co(4-CF3-C6F4)(CO)2(PMe3)2] (6) and with bromobenzene via one-electron oxidative addition of the C−Br bond to give the cobalt(II) bromide [CoBr(4-CF3-C6F4)(PMe3)3] (8) and a C−C-coupling product, 4-phenylheptafluorotoluene (7). The structures of complexes 1, 4, and 8 were determined by X-ray crystallography.

Activation of sp3 Carbon−Hydrogen Bonds by Cobalt and Iron Complexes and Subsequent C−C Bond Formation

Co-reporter:Guoqiang Xu, Hongjian Sun and Xiaoyan Li

Organometallics 2009 Volume 28(Issue 20) pp:6090-6095

Publication Date(Web):September 9, 2009

DOI:10.1021/om9007218

The sp3 C−H bond activation induced by CoMe(PMe3)4 and FeMe2(PMe3)4 was investigated. C(sp3)-cyclometalated complexes, based on diphosphinito PCP ligand (Ph2POCH2)2CH2, Co{(Ph2POCH2)2CH}(PMe3)2 (1), and Fe{(Ph2POCH2)2MeC}(H)(PMe3)2 (2), were obtained under mild conditions. Iodomethane is oxidatively added to 1, affording Co{(Ph2POCH2)2CH}(PMe3)(Me)(I) (3). Monocarbonylation of the hydrido-iron complex 2 occurs with substitution of a trimethylphosphine ligand trans to the hydrido ligand, affording Fe{(Ph2POCH2)2MeC}(H)(CO)(PMe3) (4). The reaction of 2 with phenylacetylene delivered the demetalated new diphosphine ligand (Ph2POCH2)2CHCH3 (6) and bis(phenylethinyl)iron complex Fe(PhCC)2(PMe3)4 (5). The new complexes 1−4 were characterized by spectroscopic methods and by X-ray diffraction analysis.

N-Assisted Carbon−Hydrogen Bond Activation by Cobalt(I) Complexes

Co-reporter:Aichen Wang, Hongjian Sun and Xiaoyan Li

Organometallics 2008 Volume 27(Issue 21) pp:5434-5437

Publication Date(Web):October 8, 2008

DOI:10.1021/om8007844

Reactions of 2-(4′-R-phenylazo)-4-methylphenols (R = Me (1), Br (2)) with Co(PMe3)3Cl afford two organocobalt(III) complexes, Co(PMe3)2Cl(Me(C6H3O∩N═NC6H3R)·(H2NC6H4R)) (R = Me (3), Br (4)), whereas the reactions of 1 and 2 with Co(PMe3)4 and Co(PMe3)4Me afford the dinuclear complex [Co2(PMe3)4(MeC6H3O∩NH)2] (7) with the cleavage of the N═N bond. Crystal structures of 3, 4, and 7 were determined by X-ray crystallography.

Cyclometalation Reactions Involving C−Cl Bond Activation of ortho-Chlorinated Substrates with Imine as Anchoring Groups by Cobalt Complexes

Co-reporter:Yue Chen, Hongjian Sun, Ulrich Flörke and Xiaoyan Li

Organometallics 2008 Volume 27(Issue 2) pp:270-275

Publication Date(Web):January 5, 2008

DOI:10.1021/om7008793

The aldazines (C6H3Cl2-2,6)CH═N−NH2 (1a) and (C6H3Cl2-2,6)CH═N−N═CH(C6H3Cl2-2,6) (1b) or the Schiff bases (C6H3Cl2-2,6)CH═N−CH3 (1c), (C6H3Cl2-2,6)CH═N(C6H5) (1d), and (C6H3Cl2-2,6)CH═N(C10H7) (1e) were obtained by condensation of 2,6-dichlorobenzaldehyde with hydrazine, methylamine, aniline, or α-naphthylamine, respectively. Treatment of 1a−1e with [CoMe(PMe3)4] resulted in oxidative addition of the C−Cl bond to afford the ortho-chelated cobalt(III) complexes [CoClMe(PMe3)2{(C6H3Clortho)-CH═N−R}] (2a−2e). The reaction of 1b,1c with [CoCl(PMe3)3] delivered the aryl Co(III) complexes 3b,3c containing a [C−Co−Cl] fragment, while Co(II) complexes [CoCl(PMe3)2((C6H3Cl-ortho)CH═N−R)] (3d,3e) were formed through the reaction of 1d or 1e with [CoCl(PMe3)3]. Under similar conditions, the ortho-chelated cobalt(III) complex [CoBrCl(PMe3)2((C6H3Cl2-2,6)CH═N−CH3)] (4c) could be isolated via the reaction of [CoBr(PMe3)3] with 1c. The crystal and molecular structures of complexes 2a, 3b, 3e, and 4c were determined by X-ray diffraction.

Facile Synthesis of Bis(isoindolinone) through Carbonylative Cyclization and Dimerization of Phenylimine with Nickel(0) Complexes

Co-reporter:Ruixia Cao, Hongjian Sun and Xiaoyan Li

Organometallics 2008 Volume 27(Issue 8) pp:1944-1947

Publication Date(Web):March 25, 2008

DOI:10.1021/om800049m

A simple and convenient synthetic method for obtaining the novel bis(isoindolinones) 2a−d starting from aryl chlorides is described, using phenylimines with stoichiometric amounts of tetrakis(trimethylphosphine)nickel(0) as starting materials under a CO atmosphere (1 bar) at room temperature. The formation mechanism was proposed and discussed. The intermediate chelate arylnickel(II) complex 5d was also isolated and structurally characterized.

An Extension of the Wittig Reaction: Attack of Phosphorus Ylides at Acyl Groups in Organocobalt Complexes

Co-reporter:Qibao Wang, Hongjian Sun, Shimin Fang, Mingcui Liu, Klaus Harms and Xiaoyan Li

Organometallics 2007 Volume 26(Issue 27) pp:6805-6811

Publication Date(Web):December 5, 2007

DOI:10.1021/om700874c

Attack of phosphorus ylides at acyl groups in organocobalt complexes was observed. Reactions of hydrido(acylenolato) cobalt(III) complexes [CoIII(O∩CO)L3H] (O∩CO = acylenolato ligand, L = P(CH3)3) 1–3 with phosphorus ylides (H2C═PPh3, H2C═P(n-Bu)3, CH3CH═PPh3) afford eight novel organocobalt compounds. The structures of the eight compounds greatly differ according to the electronic and steric properties of the reactants. As a result of the Wittig reaction compounds [CoI(O∩═)L3], 4–6 and 9 are (π-olefin)cobalt(I) compounds. Compound [CoII(O∩CO)L3] 8 is a stable (acylenolato)cobalt(II) complex with 17 valence electrons. The dinuclear compounds [CoII(O∩CO)L2]2 10–12 show unusual properties, as they are diamagnetic in solid state and possess centrosymmetric structures containing a [Co(μ2-O)]2 ring, while in solution they are mononuclear and paramagnetic. The crystal structures of the compounds 4–6, 8, 9, and 11 were determined by X-ray diffraction. The mechanisms of formation are discussed.

Reactions of Trimethylphosphane-Supported Cobalt Complexes with Salicylaldimines – Formation and Structures of Cobalt Compounds Containing Salicylaldiminato [N:O] Ligands

Co-reporter:Xiaoyan Li;Fengli Yu;Hongjian Sun;Liye Huang;Haoqing Hou

European Journal of Inorganic Chemistry 2006 Volume 2006(Issue 21) pp:

Publication Date(Web):8 SEP 2006

DOI:10.1002/ejic.200600489

The reactions of low-valent cobalt complexes CoMe(PMe₃)₄, CoCl(PMe₃)₃ and Co(PMe₃)₄ with salicylaldimines are described to give tetrahedral complexes 7–12, an octahedral complex 13 and a π-coordinated imine complex 15. The crystal structures of 13 and 15 are reported. The formation and likely mechanisms are discussed. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Novel stable five-coordinate diorgano cobalt(III) complexes: Formation, structure, and reaction with carbon monoxide

Co-reporter:Xiaoyan Li, Fengli Yu, Hongjian Sun, Haoqing Hou

Inorganica Chimica Acta 2006 Volume 359(Issue 10) pp:3117-3122

Publication Date(Web):1 July 2006

DOI:10.1016/j.ica.2006.03.029

A series of new five-coordinate acyl vinyl cobalt(III) complexes Co{η1-C(CCPh)CHPh}[C(O)CCO] L2(L = PMe3) (6–10) were prepared via formal insertion of diphenylbutadiyne into Co–H function of mer-octahedral hydrido-acyl(phenolato)-cobalt(III) complexes. The complexes are diamagnetic. One square pyramidal structure of complex 6 was confirmed by X-ray diffraction analysis. These complexes are stable in solid state. In solution, six-coordinate acyl vinyl carbonyl cobalt(III) complex 11 is approved through the reaction of complex 7 with CO and the structure of complex 11 was determined by X-ray method.Five-coordinate acyl vinyl cobalt(III) complexes Co{η1-C(CCPh)CHPh}[C(O)CCO] L2 (L = PMe3) (6–10) through the formal insertion of diphenylbutadiyne into Co–H function of mer-octahedral hydrido acyl(phenolato)-cobalt(III) complexes are reported. In solution, hexa-coordinate acyl vinyl carbonyl cobalt(III) complex 11 is approved through the reaction of complex 7 with CO. The structures of complexes 6 and 11 were determined by X-ray method.

Synthesis of dimethylcobalt(III) complexes containing trimethylphosphine and 2-formyl-phenolato- or 2-formyl-enolato(O:O) ligands

Co-reporter:Xiaoyan Li, Hongjian Sun, Alexandra Brand, Hans-Friedrich Klein

Inorganica Chimica Acta 2005 Volume 358(Issue 12) pp:3329-3333

Publication Date(Web):1 August 2005

DOI:10.1016/j.ica.2005.05.016

Substituted salicylaldehydes [C6HR1R2R3(CHO)(OH)] react with CoMe3(PMe3)3 to afford 6-coordinate (cis-dimethyl)(2-formyl-phenolato)trans-bis(trimethylphosphine)cobalt(III) compounds Co[C6HR1R2R3(CHO)(O)Me2](PMe3)2 (1: R1 = H; R2 = Me; R3 = tert-Bu; 2: R1, R2 = C6H4; R3 = H). Accordingly, substituted enolated malonic dialdehydes (CHO–CR4CR5–OH) react with CoMe3(PMe3)3 to afford 6-coordinate (cis-dimethyl)(2-formyl-enolato)trans-bis(trimethylphosphine)cobalt(III) compounds Co[(CHO–CR4CR5–O)(Me)2](PMe3)2 (3: R4, R5 = (CH2)2C6H4; 4: R4 = R5 = C6H5). In the molecular structure of 4, the cobalt atom is centred in an octahedral coordination geometry brought about by a six-membered chelate ring (O:O-ligand), cis-dimethyl and trans-trimethylphosphine groups. A reaction mechanism is suggested.Reactions of substituted salicylaldehydes and substituted malonic dialdehydes with CoMe3(PMe3)3 afford formyl(cis-dimethyl)phenolato and enolato cobalt(III) compounds. The X-ray structure of complex 4 shows an octahedral coordination geometry.

Efficient reductive dehydration of primary amides to nitriles catalyzed by hydrido thiophenolato iron(II) complexes under hydrosilation conditions

Co-reporter:Benjing Xue, Hongjian Sun, Yan Wang, Tingting Zheng, Xiaoyan Li, Olaf Fuhr, Dieter Fenske

Catalysis Communications (5 November 2016) Volume 86() pp:148-150

Publication Date(Web):5 November 2016

DOI:10.1016/j.catcom.2016.08.024

•Hydrido thiophenolato iron(II) complexes.•The reductive dehydration of amides to nitriles.•(EtO)3SiH as a reducing agent.The reductive dehydration of amides to nitriles under hydrosilation conditions with hydrido thiophenolato iron(II) complexes [cis-Fe(H)(SAr)(PMe3)4] (1–4) as catalysts is reported using (EtO)3SiH as an efficient reducing agent in the yields up to 93%. The merits of this catalytic system, the low catalyst loadings (2 mol%) and the amount of efficient reducing agent (EtO)3SiH, make this method more attractive.Download high-res image (84KB)Download full-size image

Catalytic hydrosilylation of carbonyl compounds by hydrido thiophenolato iron(II) complexes

Co-reporter:Benjing Xue, Hongjian Sun, Qingfen Niu, Xiaoyan Li, Olaf Fuhr, Dieter Fenske

Catalysis Communications (5 May 2017) Volume 94() pp:23-28

Publication Date(Web):5 May 2017

DOI:10.1016/j.catcom.2017.02.008

•Hydrosilylation of aldehyde and ketone was catalyzed by iron(II) hydride.•Reduction of aldehyde and ketone was studied with (EtO)3SiH as reducing agent.•α,β-Unsaturated carbonyl compound was reduced to α,β-unsaturated alcohols.The hydrosilylation of aldehydes and ketones under mild conditions with hydrido thiophenolato iron(II) complexes [cis–Fe(H)(SAr)(PMe3)4] (1–4) as catalysts is reported using (EtO)3SiH as an efficient reducing agent in the yields up to 95%. Among them complex 1 is the best catalyst. Complex 1 could also be used as catalyst to reduce the α,β-unsaturated carbonyl compounds selectively to the α,β-unsaturated alcohols in high yields.

Reactions of iron(II) hydrides formed by selective CF/CH bond activation in fluoroaryl-imines

Co-reporter:Lin Wang, Hongjian Sun, Zhenyu Zuo, Benjing Xue, Xiaoyan Li, Olaf Fuhr, Dieter Fenske

Inorganica Chimica Acta (1 May 2017) Volume 461() pp:

Publication Date(Web):1 May 2017

DOI:10.1016/j.ica.2017.02.009

•Hydrido iron complexes were synthesized.•Reactions of hydrido iron complexes with acids were studied.•Trimethylsilylacetylenyl iron(II) complexes were prepared.In this paper the reactions of iron(II) hydrides 6–10 formed by selective CF/CH bond activation in fluoroaryl-imines were reported. Iron hydrides 6 and 7 reacted with haloalkane to give rise to the corresponding iron halides 11 and 12 with the mer-rearrangement of the three trimethylphosphine ligands. The related trifluoromethylcarboxyl iron complexes 13 and 14 with the carboxyl group as monodentate ligand were obtained from the reactions of hydrides 8 and 9 with F3CCOOH. The reaction of iron hydride 6 with Lewis acid LiBF4 delivered ionic iron complex 15. Both the reaction of iron hydride 10 with Me3SiCCH and the reaction of iron bromide 11 with Me3SiCCLi could provide the derivative trimethylsilylacetylenyl iron(II) complexes 16 and 17 respectively. The molecular structures of complexes 12, 13 and 17 were determined by single crystal X-ray diffraction.The reactions of iron(II) hydrides formed by selective CF/CH bond activation in fluoroaryl-imines were reported.

Reactivity of mer-hydrido(2-mercaptobenzoyl)tris(trimethylphosphine)cobalt(III) complex

Co-reporter:Qingfen Niu, Hongjian Sun, Lin Wang, Qingping Hu and Xiaoyan Li

Dalton Transactions 2014 - vol. 43(Issue 10) pp:NaN4066-4066

Publication Date(Web):2013/11/28

DOI:10.1039/C3DT52519H

The selective activation of a C–F bond with an auxiliary strong Lewis acid: a method to change the activation preference of C–F and C–H bonds

Co-reporter:Lin Wang, Hongjian Sun, Xiaoyan Li, Olaf Fuhr and Dieter Fenske

Dalton Transactions 2016 - vol. 45(Issue 45) pp:NaN18141-18141

Publication Date(Web):2016/10/13

DOI:10.1039/C6DT03235D

The selective activation of the C–F bonds in substituted (2,6-difluorophenyl)phenylimines (2,6-F2H3C6-(CNH)-n′-R-C6H4 (n′ = 2, R = H (1); n′ = 2, R = Me (2); n′ = 4, R = tBu (3))) by Fe(PMe3)4 with an auxiliary strong Lewis acid (LiBr, LiI, or ZnCl2) was explored. As a result, iron(II) halides ((H5C6-(CNH)-2-FH3C6)FeX(PMe3)3 (X = Br (8); Cl (9)) and (n-RH4C6-(CNH)-2′-FH3C6)FeX(PMe3)3 (n = 2, R = Me, X = Br (11); n = 4, R = tBu, X = I (12))) were obtained. Under similar reaction conditions, using LiBF4 instead of LiBr or ZnCl2, the reaction of (2,6-difluorophenyl)phenylimine with Fe(PMe3)4 afforded an ionic complex [(2,6-F2H3C6-(CNH)-H4C6)Fe(PMe3)4](BF4) (10) via the activation of a C–H bond. The method of C–F bond activation with an auxiliary strong Lewis acid is appropriate for monofluoroarylmethanimines. Without the Lewis acid, iron(II) hydrides ((2-RH4C6-(CNH)-2′-FH3C6)FeH(PMe3)3 (R = H (13); Me (14))) were generated from the reactions of Fe(PMe3)4 with the monofluoroarylmethanimines (2-FH4C6-(CNH)-2′-RC6H4 (R = H (4); Me (5))); however, in the presence of ZnCl2 or LiBr, iron(II) halides ((2-RH4C6-(CNH)-H4C6)FeX(PMe3)3 (R = H, X = Cl (15); R = Me, X = Br (16))) could be obtained through the activation of a C–F bond. Furthermore, a C–F bond activation with good regioselectivity in (pentafluorophenyl)arylmethanimines (F5C6-(CNH)-2,6-Y2C6H3 (Y = F (6); H (7))) could be realized in the presence of ZnCl2 to produce iron(II) chlorides ((2,6-Y2H3C6-(CNH)-F4C6)FeCl(PMe3)3 (Y = F (17); H (18))). This series of iron(II) halides could be used to catalyze the hydrosilylation reaction of aldehydes. Due to the stability of iron(II) halides to high temperature, the reaction mixture was allowed to be heated to 100 °C and the reaction could finish within 0.5 h.

Imine-assisted C–F bond activation by electron-rich iron complexes supported by trimethylphosphine

Co-reporter:Xiaofeng Xu, Hongjian Sun, Yujie Shi, Jiong Jia and Xiaoyan Li

Dalton Transactions 2011 - vol. 40(Issue 31) pp:NaN7872-7872

Publication Date(Web):2011/07/07

DOI:10.1039/C1DT10843C

Hydrosilylation of aldehydes and ketones catalyzed by hydrido iron complexes bearing imine ligands

Co-reporter:Zhenyu Zuo, Hongjian Sun, Lin Wang and Xiaoyan Li

Dalton Transactions 2014 - vol. 43(Issue 30) pp:NaN11722-11722

Publication Date(Web):2014/06/03

DOI:10.1039/C4DT00944D

Selective activation of C–F and C–H bonds with iron complexes, the relevant mechanism study by DFT calculations and study on the chemical properties of hydrido iron complex

Co-reporter:Xiaofeng Xu, Jiong Jia, Hongjian Sun, Yuxia Liu, Wengang Xu, Yujie Shi, Dongju Zhang and Xiaoyan Li