Co-reporter:Bin Li, Jiancheng Li, Rui Liu, Hongping Zhu, and Herbert W. Roesky
Inorganic Chemistry March 20, 2017 Volume 56(Issue 6) pp:3136-3136
Publication Date(Web):March 7, 2017
DOI:10.1021/acs.inorgchem.7b00012
Heterobimetallic aluminum–copper and aluminum–zinc clusters were prepared from the reaction of LAl(SeH)2 [1; L = HC(CMeNAr)2 and Ar = 2,6-iPr2C6H3] with (MesCu)4 and ZnEt2, respectively. The resulting clusters with the core structures of Al2Se4Cu4 and Al2Se4Zn3 exhibit unique metal–organic frameworks. This is a novel pathway for the synthesis of aluminum–copper and aluminum–zinc selenides. The products have been characterized by spectroscopic methods and single-crystal X-ray structural characterization.
Co-reporter:Shuang Ding, Jiancheng Li, Rui Liu, Gang Fu, Hongping Zhu, Weiping Liu, and Qingsong Ye
ACS Omega June 2017? Volume 2(Issue 6) pp:2405-2405
Publication Date(Web):June 1, 2017
DOI:10.1021/acsomega.7b00236
The N-geminal P/Al Lewis pair [Ph2PN(2,6-iPr2C6H3)AlEt2]2 (1) has been prepared and studied for reaction with a series of alkynes. The reaction of 1 with RC≡CR yielded zwitterionic C2PNAl-heterocyclopentene [Ph2PN(2,6-iPr2C6H3)AlEt2](CR═CR) (R = Me (2), Ph (3)); with PhC≡CEt produced two isomers, [Ph2PN(2,6-iPr2C6H3)AlEt2](CPh═CEt) (4a) and [Ph2PN(2,6-iPr2C6H3)AlEt2](CEt═CPh) (4b); and with other alkynes generated [Ph2PN(2,6-iPr2C6H3)AlEt2](CR1═CR2) (R1, R2 = CO2Et, Ph (5); SiMe3, Ph (6); PPh2, Ph (7); SiMe3,H (8); H, EtO (9)). Natural bond orbital analysis of the charge separation of the C≡C bond of alkynes was carried out, and then, the electronic matching interaction mode between the combined Lewis acid (AlEt2) and base (PPh2) groups of 1 and the C≡C bond of such alkynes was discussed. Reactions of 1 with alkene, nitrile, and carbodiimide molecules were also carried out, and cycloaddition compounds 10–12 were produced.
Co-reporter:Bin Li;Subrata Kundu;Helena Keil;Regine Herbst-Irmer;Dietmar Stalke;Gernot Frenking;Diego M. Andrada;Herbert W. Roesky
Chemical Communications 2017 vol. 53(Issue 17) pp:2543-2546
Publication Date(Web):2017/02/23
DOI:10.1039/C7CC00325K
The reaction of LAl: (L = HC[C(Me)N(Ar)]2, Ar = 2,6-iPr2C6H3) and cAAC:→AlX3 (X = Cl, I) (cAAC = cyclic alkyl amino carbene) results in strikingly asymmetric Al(II)–Al(II) compounds LAl(X)–Al(X)2–cAAC [X = Cl (2a); I (2b)]. In these dialuminum(II) compounds the two Al atoms bear different ligand environments. For a detailed insight into the structures, theoretical calculations were carried out.
Co-reporter:Peng Nie;Yan Li;Qian Yu;Bin Li;Ting-Bin Wen
European Journal of Inorganic Chemistry 2017 Volume 2017(Issue 33) pp:3892-3899
Publication Date(Web):2017/09/08
DOI:10.1002/ejic.201700607
The reaction of the β-diketiminatochlorogermylene L(Cl)Ge {1, L = HC[C(Me)N-2,6-iPr2C6H3]2} with Ru3(CO)12 in molar ratios of 3:1 or 6:1 led to the Ge2Ru complex [L(Cl)Ge]2Ru(CO)3 (3). A speculative GeRu intermediate, L(Cl)GeRu(CO)4, was detected when the reaction was monitored by 1H NMR spectroscopy at elevated temperatures. The formation of this intermediate was supported by similar monitoring of the reaction of L(PhC≡C)Ge (2) with Ru3(CO)12 by 1H NMR spectroscopy and the isolation of a mixture of L(PhC≡C)GeRu(CO)4 (4) and [L(R)Ge]2Ru(CO)3 (5) from this reaction in a molar ratio of 3:1 as well as the clean formation of 5 from such a reaction in a 6:1 molar ratio. Complex 3 reacted with LiHBEt3 through an unusual Cl/Et metathesis to give L(Et)GeRu(CO)4 (6). However, the reaction of 3 with LiN(SiMe3)2 resulted in the base-assisted dehydrochlorination involving one methyl group of each L ligand backbone and the chlorine atom at the Ge center to yield [L′Ge]2Ru(CO)3 {7, L′ = HC[C(Me)N-2,6-iPr2C6H3][C(CH2)N-2,6-iPr2C6H3]}. The further reaction of 7 with a stoichiometric amount of H2O afforded L(HO)GeRu(CO)4 (8) through a 1,4-dipolar addition across the L′Ge functionality. In addition, the reaction of 3 with I2 occurred through an oxidative addition at the Ru center to generate L(Cl)GeRuI2(CO)3 (10).
Co-reporter:Xiaoping Wang, Jiancheng Li, Shimin Chen, Weiping Liu, Qingsong Ye and Hongping Zhu
Dalton Transactions 2016 vol. 45(Issue 15) pp:6709-6717
Publication Date(Web):02 Mar 2016
DOI:10.1039/C6DT00059B
Aryl(silyl)amino group stabilized hydridosilanediols RSiH(OH)2 (R = N(SiMe2Ph)-2,6-iPr2C6H3 (4), N(SiMe3)-2,6-iPr2C6H3 (5), and N(SiMe2Ph)-2,4,6-Me3C6H2 (6)) were prepared from the controlled hydrolysis of the related RSiHCl2 (1–3) each in the presence of aniline as the HCl acceptor. Reactions of 4 with AlMe3, AliBu3, AlH(iBu)2, and AlH3·NMe3, respectively, yielded alumino(hydrido)siloxanes [2,6-iPr2C6H3N(SiMe2Ph)Si(H)OAlMe(THF)]2 (7), [2,6-iPr2C6H3N(SiMe2Ph)Si(H)OAliBu(THF)]2 (9), [2,6-iPr2C6H3N(SiMe2Ph)Si(H)O2]3[Al(THF)]2 (10), and [2,6-iPr2C6H3N(SiMe2Ph)Si(H)OAlH(THF)]2 (11). The reaction of 5 with AlMe3 gave [2,6-iPr2C6H3N(SiMe3)Si(H)OAlMe(THF)]2 (8), a compound similar to 7. Compounds 1–11 are characterized by NMR (1H, 13C, and 29Si) and IR spectroscopy and CHN elemental analysis, of which 6 and 8–11 are further studied by X-ray crystallography. Compounds 8–9 and 11 feature cyclic structures all with the skeleton core of Si2O4Al2 while compound 10 exhibits a bicyclic structure having a core of Si3O6Al2. Melting point measurements indicated that 4–6 are thermally stable bearing the geminal SiH and SiOH groups. Compounds 8–9 and 11 are thermally stable as well with the O atom-bridged SiH and AlR (R = Me, iBu, or H) groups.
Co-reporter:Ying Yu, Jiancheng Li, Weiping Liu, Qingsong Ye and Hongping Zhu
Dalton Transactions 2016 vol. 45(Issue 14) pp:6259-6268
Publication Date(Web):02 Dec 2015
DOI:10.1039/C5DT03873A
Amino group combined P/Ge-based frustrated Lewis pairs (FLPs) Ph2PN(R)GeCl3 (R = 2,6-iPr2C6H3 (1), 2,4,6-Me3C6H2 (2), and C6H11 (3)) and Ph2PN(2,6-iPr2C6H3)GeMe3 (4) as well as P/Sn-based FLP Ph2PN(2,6-iPr2C6H3)SnMe3 (5) were prepared and utilized for reactions with alkyne and aldehyde molecules. Compounds 1–3 each reacted with MeO2CCCCO2Me to give zwitterionic cyclic vinyls [Ph2PN(R)GeCl3](MeO2CCCCO2Me) (6–8) and compound 1 reacted with HCCCO2Me to give the similar compound [Ph2PN(2,4,6-Me3C6H2)GeCl3](HCCCO2Me) (9). Compound 4 reacted with RCCCO2Me to afford acyclic vinyls 2,6-iPr2C6H3NP(Ph2)C(R)C(CO2Me)GeMe3 (R = CO2Me (10), H (11)) and 5 reacted with MeO2CCCCO2Me to give 2,6-iPr2C6H3NP(Ph2)C(CO2Me)C(CO2Me)SnMe3 (12). The reactions of 1 with CH3CH2CHO and 1,4-(CHO)2C6H4 were also investigated and yielded novel zwitterionic OCPNGe five-heteroatom cycles [Ph2PN(2,6-iPr2C6H3)GeCl3][CH(CH2CH3)O] (13) and [Ph2PN(2,6-iPr2C6H3)GeCl3][p-(OCH)C6H4CHO][Cl3GeN(2,6-iPr2C6H3)PPh2] (14). Compounds 1–14 were characterized by NMR (1H, 13C, and 31P) and CHN elemental analysis, of which 1, 7, and 10–14 were further studied by X-ray crystallography. The reactions of 4 (or 5) with RCCCO2Me to produce 10–12 present a novel way of obtaining the germyl (or stannyl) and iminophosphoranyl co-substituted vinyls.
Co-reporter:Xiaolong Fang, Chunyan Zhang, Jin Chen, Hongping Zhu and Youzhu Yuan
RSC Advances 2016 vol. 6(Issue 51) pp:45512-45518
Publication Date(Web):04 May 2016
DOI:10.1039/C6RA00320F
A series of new ruthenium complexes with rigid ligand o-(diphenylphosphino)aniline, including [(PPh3)(o-PPh2C6H4NH2)RuCl2]2 (1), (o-PPh2C6H4NH2)2RuCl2 (2), [(o-PPh2C6H4NH2)2(o-PPh2C6H4NH)Ru]+Cl− (3), Ph3P(η2-H2)Ru(μ-H)(μ-o-PPh2C6H4NH)2RuH(PPh3) (4), (o-PPh2C6H4NH2)(o-PPh2C6H4NH)RuCl(CO) (5), (o-PPh2C6H4NH2)(o-PPh2C6H4NH)RuH(CO) (6), and [(o-PPh2C6H4NH)2Ru(CO)]2 (7) were synthesized and employed as catalysts for chemoselective hydrogenation of esters. Among them, complexes 1, 2, and 5 exhibited excellent performance in hydrogenation of dimethyl oxalate to methyl glycolate, in comparison with the ruthenium complexes with a flexible aminophosphine ligand, such as (Ph2P(CH2)2NH2)2RuCl2, (Ph2P(CH2)3NH2)2RuCl2, and (o-Ph2PC6H4CH2NH2)2RuCl2, under identical conditions. Complexes 1 and 2 also displayed good activities in the hydrogenation of other aliphatic and cyclic esters. The catalytic mechanism of hydrogenation was discussed according to the results of NMR spectroscopic studies and control experiments.
Co-reporter:Bin Li, Chunyan Zhang, Ying Yang, Hongping Zhu, and Herbert W. Roesky
Inorganic Chemistry 2015 Volume 54(Issue 13) pp:6641-6646
Publication Date(Web):June 18, 2015
DOI:10.1021/acs.inorgchem.5b00990
The β-diketiminato aluminum-monohydroxide and -dihydroxide were reacted with tetrameric (CuMes)4 (Mes = 2,4,6-Me3C6H2) to prepare Cu(I) complexes bearing the Al–O–Cu moiety. All complexes are characterized by elemental analysis, nuclear magnetic resonance, and single-crystal X-ray diffraction. The reaction of aluminum–monohydroxide LAlR(OH) (L = HC[C(Me)N(Ar)]2; Ar = 2,6-iPr2C6H3; R = Me, Et) with (CuMes)4 afforded the Cu(I) alumoxane [LAl(R)OCu·MesCu]2 (R = Me, 1; Et, 2). Using the aluminum-dihydroxide LAl(OH)2 as the precursor, the dimeric [LAl(OH)OCu·MesCu]2 (3) was isolated, bearing one reactive OH group on each Al center. When the reaction of LAl(OH)2 with (CuMes)4 was carried out at 70 °C, the dimeric octanuclear Cu(I) compound [LAl(OCu·MesCu)2]2 (4) was formed, where two residual Mes groups are located at the neighboring position on each of the two (OCu·MesCu)2 squares. Compound 4 can be alternatively obtained by reacting 3 with 1 equiv of (CuMes)4 to demonstrate the stepwise assembly of the Cu(I) alumoxanes.
Co-reporter:Jiancheng Li, Yan Li, Indu Purushothaman, Susmita De, Bin Li, Hongping Zhu, Pattiyil Parameswaran, Qingsong Ye, and Weiping Liu
Organometallics 2015 Volume 34(Issue 17) pp:4209-4217
Publication Date(Web):April 20, 2015
DOI:10.1021/om501288t
Reactions of the N-aryl(diphenylphosphanyl)aminosilane Ph2PN(Ar)SiCl3–nMen (Ar = 2,4,6-Me3C6H2, n = 0 (1a), 1 (2a), 2 (3a), 3 (4a); Ar = 2,6-iPr2C6H3, n = 0 (1b), 1 (2b), 2 (3b), 3 (4b)) with methyl propiolate and dimethyl acetylenedicarboxylate (DMAD) give two types of products, the zwitterionic heterocycles [Ph2PN(2,4,6-Me3C6H2)SiCl3](HC═CCO2Me) (5c) and [Ph2PN(Ar)SiCl3–nMen](MeO2CC═CCO2Me) (Ar = 2,4,6-Me3C6H2, n = 0 (5a), 1 (6a), 2 (7a); Ar = 2,6-iPr2C6H3, n = 0 (5b), 1 (6b), 2 (7b)) and (Z)-silyliminophosphoranylalkene ArN═P(Ph2)C(CO2Me)═C(CO2Me)SiMe3 (Ar = 2,4,6-Me3C6H2 (8a), 2,6-iPr2C6H3 (8b)). The reaction of Ph2PN(SiMe3)2 with DMAD gives only the acyclic alkene Me3SiN═P(Ph2)(MeO2C)C═C(CO2Me)SiMe3 (9), which is similar to 8a,b. In these reactions, compounds 1a–4a and 1b–4b behave as N-geminal P/Si-based Lewis pairs, which undergo a dipolar cycloaddition reaction with the alkyne. The theoretical calculations indicate that the reactions proceed through a concerted cycloaddition reaction mechanism. The stability of these heterocycles decreases as the number of the Me substituent on the pentacoordinated Si atom increases. When the Si center is substituted with three Me groups (4a,b), the heterocyclic intermediates undergo ring opening by Si–N bond cleavage and concomitant N═P bond formation resulting in 8a,b. The formation of the acyclic (Z)-alkene (8a,b and 9) can be considered as a stepwise SN2 reaction at the silicon center.
Co-reporter:Bin Li;Pan Zhou;Yuefei Chen;Biao Jiang
Science China Chemistry 2015 Volume 58( Issue 1) pp:107-113
Publication Date(Web):2015 January
DOI:10.1007/s11426-014-5247-z
Synthesis and anionic polymerization of the fluorine-substituted phenyl methacrylates are herein reported. A series of mono-, di-, and multi-substituted fluorophenyl methacrylates H2C=C(CH3)C(O)OC6H4F-4 (M1a), H2C=C(CH3)C(O)OC6H4F-3 (M1b), H2C=C(CH3)C(O)OC6H3F2-2,4 (M2), H2C=C(CH3)C(O)OC6H2F3-2,3,4 (M3), H2C=C(CH3)C(O)OC6HF4-2,3,5,6 (M4), and H2C=C(CH3)C(O)OC6F5 (M5) were synthesized and characterized. Initially, the polymerization was carried out on the monomer M1a by using nBuLi, tBuLi, and KH as the respective catalysts; this approach produced the polymers in yields of 12%–50%, but with lower molecular weights. Similar results were obtained by using tBuLi for catalytically polymerizing the other five monomers. By introducing a co-catalyst MeAl(BHT)2, the catalysts NaH, LiH, and tBuOLi each were tested to polymerize M1a, which gave the polymers in very low yields (3%–7%). Polymer yields of 13%–27% were obtained by each of the catalysts LiAlH4, nBuLi, PhLi, and tBuLi in connection with MeAl(BHT)2, but a better yield (61%) was achieved with KH/MeAl(BHT)2. The KH/MeAl(BHT)2 catalyst system was further employed to polymerize M1b and M2, which afforded respective polymer yields of 12%–63% and 10%–53%, depending on the molar ratios of KH:MeAl(BHT)2 as well as on the monomer concentrations. All of the polymers produced were syndiotactically rich in structure, as indicated by either 1H or 19F NMR data. The polymerization mechanism by the combined catalyst system is proposed.
Co-reporter:Bin Li; Jiancheng Li; Herbert W. Roesky
Journal of the American Chemical Society 2014 Volume 137(Issue 1) pp:162-164
Publication Date(Web):December 19, 2014
DOI:10.1021/ja511722a
The synthesis of heterobimetallic cluster with the Al–S–M (M = Cu and Ag) structural unit has been realized for the first time by the reaction of aluminum-dithiol LAl(SH)2 (L = HC[C(Me)N(Ar)]2, Ar = 2,6-iPr2C6H3) with (MesCu)4 and (MesAg)4 (Mes = 2,4,6-Me3C6H2), respectively. The isolated clusters exhibit core structures of Al2Cu4S4 and Al4Ag8S8, respectively. During the formation of the [LAl(SAg)2]4, a side product of LAlS6 is formed. However, the reaction of LAl(SH)2 with excess of sulfur and (MesAg)4 resulted in the formation of LAlS4 as the only product soluble in organic solvents. Both of them represent rare examples of aluminum polysulfides. All compounds were characterized by spectroscopic methods and single crystal X-ray diffraction studies.
Co-reporter:Yan Li, Hongping Zhu, Diego M. Andrada, Gernot Frenking and Herbert W. Roesky
Chemical Communications 2014 vol. 50(Issue 35) pp:4628-4630
Publication Date(Web):10 Mar 2014
DOI:10.1039/C4CC00912F
An interesting aminosilanetrithiol RSi(SH)3 (R = N(SiMe3)-2,6-iPr2C6H3) has been prepared by the reaction of lithium aminosilanetrithiolate {RSi[SLi(THF)]3}2 with MeCOOH. Theoretical calculations indicate that the LP(N) → σ*(Si–S) and LP(S) → σ*(Si–S) electron donations remarkably contribute to the stabilization of the Si(SH)3 part of the molecule. RSi(SH)3 is the first example of a stable molecule containing three SH groups attached to one element.
Co-reporter:Yan Li, Kartik Chandra Mondal, Peter Stollberg, Hongping Zhu, Herbert W. Roesky, Regine Herbst-Irmer, Dietmar Stalke and Heike Fliegl
Chemical Communications 2014 vol. 50(Issue 25) pp:3356-3358
Publication Date(Web):03 Feb 2014
DOI:10.1039/C4CC00251B
Reaction of the monoanionic radical salt IP˙−K+ (IP = (Py)CH(=NR); Py = C5H4N, R = 2,6-iPr2C6H3; α-iminopyridine) with GeCl2(dioxane) afforded compound (IPGeCl)2 (1) which produced red blocks of IPGe: (2), when treated with KC8 in toluene. 1 is a digermylene formed via C–C coupling between two carbon-centered radicals. 2 can be considered as an analogue of a N-heterocyclic carbene, which exhibits a five-membered GeC2N2 ring with one CC double bond. 2 is formed by two-electron reduction of 1 with cleavage of the two Ge–Cl bonds and the central C–C single bond.
Co-reporter:Yan Li, Kartik Chandra Mondal, Jens Lübben, Hongping Zhu, Birger Dittrich, Indu Purushothaman, Pattiyil Parameswaran and Herbert W. Roesky
Chemical Communications 2014 vol. 50(Issue 23) pp:2986-2989
Publication Date(Web):14 Jan 2014
DOI:10.1039/C3CC49635J
(cAAC)Ge(GeL)2 (1) (cAAC = cyclic alkyl(amino) carbene; L = PhC(tBuN)2), a functionalized Ge3-compound was prepared. Quantum mechanical studies on 1 show a reciprocal relationship between the electronic state of the central tri-coordinated Ge atom and its reactivity towards protons, viz. tetravalent Ge(0) in terms of bonding and divalent Ge(0) in terms of reactivity. Thus the central Ge atom can be considered as having a hidden but highly reactive lone pair of electrons. However, the terminal Ge atoms can be considered as tri-coordinated divalent Ge(I) with an active lone pair of electrons.
Co-reporter:Bin Li, Yan Li, Na Zhao, Yuefei Chen, Yujue Chen, Gang Fu, Hongping Zhu and Yuqiang Ding
Dalton Transactions 2014 vol. 43(Issue 31) pp:12100-12108
Publication Date(Web):22 May 2014
DOI:10.1039/C4DT00937A
β-Diketiminato cyclopentadienyl and ferrocenylethynyl germylenes LGeR (L = HC[C(Me)N-2,6-iPr2C6H3]2, R = Cp (1) and CCFc (2)) were prepared and utilized to synthesize the GeTe bond species. Reactions of 1, 2, and LGeCCPh (3) with an excess of Te powder proceeded in toluene under reflux successfully yielded germanetellurone L(R)GeTe (R = Cp (4), CCFc (5), and CCPh (6)). Further reaction of 4 with GeCl2·dioxane at −78 °C resulted in L(Cp)GeTe(GeCl2) (7), the first example of a germylene germanetellurone adduct. Both compounds 4 and 7 contain two isomers that are generated by the simultaneous 1,2-H- and 1,3-H-shifts over the Cp ring at the Ge atom. The reactions of L(Me)GeE with AuC6F5·SC4H8 at room temperature led to pentafluorophenyl gold(I) germanethione and germaneselone compounds L(Me)GeE(AuC6F5) (E = S (8) and Se (9)). The formation of compounds 7–9 exhibits a rare nucleophilic coordination reaction pathway by the GeE (E = S, Se, Te) bond towards the metal-containing Lewis acidic species. The structures of compounds 1, 2, and 4–9 are studied by the NMR and/or IR spectroscopy and X-ray crystallography.
Co-reporter:Yan Li;Dr. Kartik Chra Mondal;Dr. Prinson P. Samuel;Dr. Hongping Zhu;Claudia M. Orben;Dr. Saravanan Panneerselvam;Priv.-Doz.Dr. Birger Dittrich;Dr. Brigitte Schwederski;Dr. Wolfgang Kaim;Totan Mondal;Dr. Debasis Koley;Dr. Herbert W. Roesky
Angewandte Chemie 2014 Volume 126( Issue 16) pp:4252-4256
Publication Date(Web):
DOI:10.1002/ange.201310975
Abstract
A neutral C4 cumulene 1 that includes a cyclic alkyl(amino) carbene (cAAC), its air-stable radical cation 1.+, and dication 12+ have been synthesized. The redox property of 1.+ was studied by cyclic voltammetry. EPR and theoretical calculations show that the unpaired electron in 1.+ is mainly delocalized over the central C4 backbone. The commercially available CBr4 is utilized as a source of dicarbon in the cumulene synthesis.
Co-reporter:Yan Li;Dr. Kartik Chra Mondal;Dr. Prinson P. Samuel;Dr. Hongping Zhu;Claudia M. Orben;Dr. Saravanan Panneerselvam;Priv.-Doz.Dr. Birger Dittrich;Dr. Brigitte Schwederski;Dr. Wolfgang Kaim;Totan Mondal;Dr. Debasis Koley;Dr. Herbert W. Roesky
Angewandte Chemie International Edition 2014 Volume 53( Issue 16) pp:4168-4172
Publication Date(Web):
DOI:10.1002/anie.201310975
Abstract
A neutral C4 cumulene 1 that includes a cyclic alkyl(amino) carbene (cAAC), its air-stable radical cation 1.+, and dication 12+ have been synthesized. The redox property of 1.+ was studied by cyclic voltammetry. EPR and theoretical calculations show that the unpaired electron in 1.+ is mainly delocalized over the central C4 backbone. The commercially available CBr4 is utilized as a source of dicarbon in the cumulene synthesis.
Co-reporter:Jinjin Wang, Rui Liu, Wenqing Ruan, Yan Li, Kartik Chandra Mondal, Herbert W. Roesky, and Hongping Zhu
Organometallics 2014 Volume 33(Issue 11) pp:2696-2703
Publication Date(Web):May 19, 2014
DOI:10.1021/om401095n
The aryl(silyl)aminotrichlorosilane 2,6-iPr2C6H3N(SiMe2Ph)SiCl3 (1) and aryl(phosphanyl)aminotrichlorosilane ArN(PPh2)SiCl3 (Ar = 2,6-iPr2C6H3 (2), 4-MeC6H4 (3), 2,4,6-Me3C6H2 (4)) were prepared and utilized for investigation in reactions with freshly prepared lithium alkynyls. Reaction of 1 with PhC≡CLi resulted in the compounds PhMe2SiC≡CPh and 2,6-iPr2C6H3N[Li(THF)3]Si(C≡CPh)3 (5), while 2 reacted with R′C≡CLi to produce the compounds Ph2PC≡CR′ and [2,6-iPr2C6H3NSi(C≡CR′)2]2 (R′ = Ph (6), tBu (7), CH2CH2Ph (8)). Reaction of 3 with PhC≡CLi led to the formation of Ph2PC≡CPh and [4-MeC6H4NSi(C≡CPh)2]3 (9a) as a major product and {4-MeC6H4NSi(C≡CPh)[N(4-MeC6H4)Si(C≡CPh)3]}2 (9b) as a minor product. When 4 was reacted with PhC≡CLi, [2,4,6-Me3C6H2NSi(C≡CPh)2]2 (10a) was isolated as the major product while [(2,4,6-Me3C6H2)3N3Si2(C≡CPh)4Li(THF)]−[Li(THF)4]+ (10b) was the minor product. The formation of Ph2PC≡CPh was also detected. All reported compounds were characterized by multinuclear NMR (1H, 13C, 29Si, and/or 31P) and/or IR spectroscopy, and compounds 2, 5–8, 9a, and 10b were further distinguished by single-crystal X-ray crystallography. These results exhibit a route to the Si2N2- or Si3N3-based cyclosilazanes 6–8, 9a, 9b, and 10a via the N–P bond cleavage of the aryl(phosphanyl)aminotrichlorosilanes during multiple metathesis reactions.
Co-reporter:Yan Li ; Kartik Chandra Mondal ; Herbert W. Roesky ; Hongping Zhu ; Peter Stollberg ; Regine Herbst-Irmer ; Dietmar Stalke ;Diego M. Andrada
Journal of the American Chemical Society 2013 Volume 135(Issue 33) pp:12422-12428
Publication Date(Web):July 19, 2013
DOI:10.1021/ja406112u
The cyclic alkyl(amino) carbene (cAAC:)-stabilized acyclic germylones (Me2-cAAC:)2Ge (1) and (Cy2-cAAC:)2Ge (2) were prepared utilizing a one-pot synthesis of GeCl2(dioxane), cAAC:, and KC8 in a 1:2:2.1 molar ratio. Dark green crystals of compounds 1 and 2 were produced in 75 and 70% yields, respectively. The reported methods for the preparation of the corresponding silicon compounds turned out to be not applicable in the case of germanium. The single-crystal X-ray structures of 1 and 2 feature the C–Ge–C bent backbone, which possesses a three-center two-electron π-bond system. Compounds 1 and 2 are the first acyclic germylones containing each one germanium atom and two cAAC: molecules. EPR measurements on compounds 1 and 2 confirmed the singlet spin ground state. DFT calculations on 1/2 revealed that the singlet ground state is more stable by ∼16 to 18 kcal mol–1 than that of the triplet state. First and second proton affinity values were theoretically calculated to be of 265.8 (1)/267.1 (2) and 180.4 (1)/183.8 (2) kcal mol–1, respectively. Further calculations, which were performed at different levels suggest a singlet diradicaloid character of 1 and 2. The TD-DFT calculations exhibit an absorption band at ∼655 nm in n-hexane solution that originates from the diradicaloid character of germylones 1 and 2.
Co-reporter:Yan Li, Jinjin Wang, Yile Wu, Hongping Zhu, Prinson P. Samuel and Herbert W. Roesky
Dalton Transactions 2013 vol. 42(Issue 37) pp:13715-13722
Publication Date(Web):05 Jul 2013
DOI:10.1039/C3DT51408K
Herein we report on the synthesis, characterization and catalytic application of metallasiloxanes of group 13–15. Reactions of R(Me)Si(OH)2 (R = N(SiMe3)-2,6-iPr2C6H3) (A) with Bi(NEt2)3, Sb(NEt2)3, Ge[N(SiMe3)2]2 and AlMe3 afforded [R(Me)SiO2BiNEt2]2 (1), [R(Me)SiO2SbOSi(OH)(Me)R]2 (2), [R(Me)SiO2]3(GeH)2 (3), and [R(Me)SiO2AlMe(THF)]2 (4), respectively. Reactions of RSi(OH)3 (B) with Bi(NEt2)3 and AlMe3 produced complexes (RSiO3Bi)4 (5) and (RSiO3)2[AlMe(THF)]3 (6). Compounds 1–6 have been characterized by IR and NMR spectroscopy, single crystal X-ray structure and elemental analysis. Each of the compounds 1, 2 and 4 features an eight-membered ring of composition Si2O4Bi2, Si2O4Sb2 and Si2O4Al2, while 3 and 6 exhibit a bicyclic structure with the respective skeletons of Si3O6Ge2 and Si2O6Al3. Compound 5 has a cubic core of Si4O12Bi4. Compounds 1–6 exhibit very good catalytic activity in the addition reaction of trimethylsilyl cyanide (TMSCN) with benzaldehyde. Compound 5 was found to be the best catalyst and its activity was probed in the reactions of TMSCN with a number of aldehydes and ketones.
Co-reporter:Na Zhao, Jinyuan Zhang, Ying Yang, Guifang Chen, Hongping Zhu, and Herbert W. Roesky
Organometallics 2013 Volume 32(Issue 3) pp:762-769
Publication Date(Web):January 24, 2013
DOI:10.1021/om300724t
Reactions of (phenylethynyl)germylene LGeC≡CPh (L = HC[C(Me)N-2,6-iPr2C6H3]2) with 0.25 equiv of (CuC6F5)4, 1 equiv of AgC6F5·MeCN, and 1 equiv of AuC6F5·SC4H8, respectively, yielded LGe(C≡CPh)CuC6F5 (1), [(LGeC≡CPh)2Ag]+[Ag(C6F5)2]− (2), and LGe(C≡CPh)AuC6F5 (3). Complexes 1–3 were characterized by IR and NMR spectroscopy and X-ray crystallography. Compound 1 shows a bonding pattern of the CuC6F5 entity by both the phenylethynyl C≡C linkage and the L ligand backbone of the γ-C atom, while 3 exhibits a bonding mode of the AuC6F5 entity at the germylene center. Compound 2 is an ionic derivative featuring the Ge–Ag donor–acceptor bond formed under redistribution of the AgC6F5 entity. Further reactions of 1 with (CuC6F5)4, AgC6F5·MeCN, and AuC6F5·SC4H8 afforded the complexes LGe(C≡CPh)(CuC6F5)(MC6F5) (M = Cu (4), Ag (5), Au (6)). Compounds 4–6 were characterized by IR and NMR spectroscopy, and 5 and 6 were further investigated by X-ray crystallography. Compounds 4–6 all show an additional bonding of the respective MC6F5 moiety at the germylene center of 1. These studies reveal a multiple donor reactivity of LGeC≡CPh. The slightly different Lewis acidic properties of the congeneric pentafluorophenylcopper(I), -silver(I), and -gold(I) complexes as acceptors are thus disclosed.
Co-reporter:Ying Yang ; Na Zhao ; Yile Wu ; Hongping Zhu ;Herbert W. Roesky
Inorganic Chemistry 2012 Volume 51(Issue 4) pp:2425-2431
Publication Date(Web):February 9, 2012
DOI:10.1021/ic202388d
Reactions of LGeCl (L = CH[C(Me)N(Ar)]2; Ar = 2,6-iPr2C6H3) with KOtBu or LiR (R = 2-thienyl, N(H)Ar, PPh2) yielded the germanium(II) compounds LGeR [R = OtBu (1), 2-thienyl (2), N(H)Ar (3), PPh2 (4)]. The reduction of (2-thienyl)2PCl with lithium afforded the diphosphane [(2-thienyl)2P]2 (5). The treatment of (2-thienyl)2PCl with LiAlH4 or KHBtBu3 led to the formation of (2-thienyl)2PH (6). The NHC-assisted reaction of LGeCl and 6 resulted in the isolation of LGeP(2-thienyl)2 (7). This is the first example where NHC is used for eliminating HCl from compounds with P–H and Ge–Cl bonds. All solid products were characterized by elemental analysis, NMR and IR spectroscopy, and single-crystal X-ray structure determination.
Co-reporter:Na Zhao, Jinyuan Zhang, Ying Yang, Hongping Zhu, Yan Li, and Gang Fu
Inorganic Chemistry 2012 Volume 51(Issue 16) pp:8710-8718
Publication Date(Web):August 6, 2012
DOI:10.1021/ic300216m
Reactions of LGeMe (L = HC[C(Me)N-2,6-iPr2C6H3]2) with 0.25 or 0.5 equiv of (CuC6F5)4 gave the products [LGe(Me)CuC6F5]2 (1) and [LGe(Me)(CuC6F5)2]2 (2), respectively. In situ formed 1 reacted with 0.5 equiv of (CuC6F5)4 to give 2 on the basis of NMR (1H and 19F) spectral measurements. Conversely, 2 was converted into 1 by treatment with 2 equiv of LGeMe. Reactions of LGeC(SiMe3)N2 with 1 or 2 equiv of AgC6F5·MeCN produced the corresponding compounds LGe[C(SiMe3)N2]AgC6F5 (3) and {LGe[C(SiMe3)N2](AgC6F5)2}2 (4). Similarly, 3 was converted into 4 by treatment with 1 equiv of AgC6F5·MeCN and 4 converted into 3 by reaction with 2 equiv of LGeC(SiMe3)N2. X-ray crystallographic studies showed that 1 contains a rhombically bridged (CuC6F5)2, while 2 has a chain-structurally aggregated (CuC6F5)4, both supported by LGeMe. Correspondingly, 3 showed a terminally bound AgC6F5 and 4 a chain-structurally aggregated (AgC6F5)4, both supported by LGeC(SiMe3)N2. Photophysical studies proved that the Ge–Cu metal–metalloid donor–acceptor bonding persists in solutions of 1 and 2 and Ge–Ag donor–acceptor bonding in solutions of 3 and 4 as a result of the clear migration of their emission bands compared to those of the corresponding starting materials. Low-temperature (−50 °C) 19F NMR spectral measurements detected dissociation of 1, 2, and 4 by the aggregation part of the CuC6F5 or AgC6F5 entities in solution. These results provide good support for pentafluorophenylcopper(I) or -silver(I) species having β-diketiminate germylene as a donor because of its remarkably electronic and steric character.
Co-reporter:Ying Yang, Na Zhao, Hongping Zhu, and Herbert W. Roesky
Organometallics 2012 Volume 31(Issue 5) pp:1958-1964
Publication Date(Web):February 22, 2012
DOI:10.1021/om201252k
(Pyrrolylaldiminato)germanium(II) chloride, LGeCl (1), was prepared by reacting LLi (L = 2-(ArN═CH)-5-tBuC4H2N; Ar = 2,6-iPr2C6H3) with 1 equiv of GeCl2·(dioxane). Treatment of LGeCl (1) with KOtBu or LiN(H)Ar yielded LGeR (R = OtBu (2), N(H)Ar (3)) by halide metathesis. (Pyrrolylaldiminato)methylaluminum chloride, LAlMe(Cl) (4), was obtained from the reaction of LLi and MeAlCl2 or by treating LH with Me2AlCl in toluene. Treatment of LH with Me2AlCl or AlCl3 in Et2O at −18 °C resulted in the 1:1 adducts LH·AlMe2Cl (5) and LH·AlCl3 (5′), respectively. Further reaction of 4 with 2 equiv of LiNEt2 led to the insertion of the NEt2 group into the C═N bond together with the elimination of LiCl, to afford L′(NEt2)AlMe(NEt2)Li(THF) (6). Similarly, treatment of 4 with 2 equiv of LiPPh2(THF)2 gave L′(PPh2)AlMe(OC4H8-PPh2)Li(THF)2 (7) accompanied by ring opening of THF. Single-crystal X-ray structure determinations revealed that 3 and 4 each contained enantiomeric pairs, while 6 and 7 each adopted a single enantiomer.
Co-reporter:Gengwen Tan and Hongping Zhu
Inorganic Chemistry 2011 Volume 50(Issue 15) pp:6979-6986
Publication Date(Web):June 23, 2011
DOI:10.1021/ic200008z
The dinuclear NNP–ligand copper(I) complex [o-N═CH(C4H3N)–PPh2C6H4]2Cu2 (1) has been synthesized by the reaction of (CuMes)4 (Mes = 2,4,6-Me3C6H2) with N-((1H-pyrrol-2-yl)-methylene)-2-(diphenylphosphino)benzenamine under an elimination of MesH. Further reaction of 1 with an excess of S8 produced a mononuclear Cu(II) complex [o-N═CH(C4H3N)–P(S)Ph2C6H4]2Cu (5) and CuS. CuS was identified by Raman spectroscopy and 1 and 5 were clearly confirmed by X-ray crystallography. The N-heterocyclic carbene was employed to react with 1 to give a mononuclear [o-N═CH(C4H3N)–PPh2C6H4]Cu{C[N(iPr)CMe]2} (2). The reactions of 2 were carried out with 1/8, 2/8, and 5/8 equiv of S8, leading to compounds [o-N═CH(C4H3N)–P(S)Ph2C6H4]Cu{C[N(iPr)CMe]2} (3), [o-N═CH(C4H3N)–P(S)Ph2C6H4]Cu (4), and 5 respectively, in which CuS was generated in the third reaction and S═C[N(iPr)CMe]2 in the latter two reactions. The clean confirmation of 2–4 demonstrates a stepwise reaction process of 1 with S8 to 5 and CuS and the N-heterocyclic carbene acts well as a trapping agent.
Co-reporter:Yan Li, ;Gengwen Tan;Tao Zhu ;Jinyuan Zhang
European Journal of Inorganic Chemistry 2011 Volume 2011( Issue 34) pp:5265-5272
Publication Date(Web):
DOI:10.1002/ejic.201100821
Abstract
The reaction of BiCl3 with LLi {L = HC[(CMe)(NAr)]2, Ar = 2,6-iPr2C6H3} in a molar ratio of 1:1 was carried out under various conditions and afforded [LBiCl(μ-Cl)]2 (1), [L′BiCl(μ-Cl)]2 [4; L′ = N(Ar)=C(Me)CH=C(NHAr)CH2], and L″Bi2Cl4 [5; L″ = N(Ar)=C(Me)CC(Me)=N(Ar)]. Compounds 1 and 4 are isomers, and a thermal conversion of 1 to 4 was realized. In this reaction system, when a little excess nBuLi and BiCl3 were used, [LBiCl(μ-Cl)Bi(nBu)Cl(μ-Cl)]2 (2) was isolated as side product after the isolation of 1. The reaction of 1 with AgOOCCF3 in the absence of light from –15 °C to room temperature generated LBi(OOCCF3)2 (3). Finally, the solvent-free reaction of BiCl3 and LH at elevated temperature (125 °C) under vacuum gave [LH2]+[BiCl4(THF)]– (6) in a low yield. The formulations of all these complexes have been confirmed by 1H and 13C NMR spectroscopy and X-ray crystallography, except for 6, which was only identified by X-ray crystallography due to its insolubility in organic solvents. These complexes exhibit versatile L ligation modes at the metal atom and reveal the complexity of the reaction between BiCl3 and LLi.
Co-reporter:Gengwen Tan ; Ying Yang ; Chenhui Chu ; Hongping Zhu ;Herbert W. Roesky
Journal of the American Chemical Society 2010 Volume 132(Issue 35) pp:12231-12233
Publication Date(Web):August 17, 2010
DOI:10.1021/ja1056104
Organic soluble 56-membered copper(I) siloxane cage compound Cu24O24Si8R8 (1, R = (2,6-iPr2C6H3)N(SiMe3)) has been synthesized and structurally characterized. It consists of a copper silica-supported structure, in which the metal ions are two-coordinate and covalently anchored onto the cage surface and the weak metal···metal d10−d10 interactions are widely full within the cage, that is active in catalyzing the Ullmann−Goldberg-type C−N coupling reaction involving aryl or 2-thienyl bromides with heterocyclic nitrogen nucleophiles. This work provides insight into homogeneous catalysis utilizing the heterogeneous structure.
Co-reporter:Dongli An;Juanjuan Wang;Ting Dong;Ying Yang;Tingbin Wen, ;Xin Lu ;Ye Wang
European Journal of Inorganic Chemistry 2010 Volume 2010( Issue 28) pp:4506-4512
Publication Date(Web):
DOI:10.1002/ejic.201000433
Abstract
Mononuclear bis(imino)arylcopper(I) N-heterocyclic carbene compound [(IPM)CuL] {1, L = 2,6-(RN=CH)2-4-tBuC6H2, R = 2,6-iPr2C6H3, IPM = C[N(iPr)CMe]2} has been synthesized, structurally characterized, and its reaction with 1-adamantyl azide investigated. The reaction of a less bulky arylcopper(I) compound [(IPM)CuPh] with the azide was also studied. The formation of the corresponding products [(IPM)CuN(1-ad)NN(L)] (2) and [(IPM)CuN(Ph)NN(1-ad)] (3) (1-ad = 1-adamantyl) reveals an aryl group transfer (L in 2 and Ph in 3) reactivity pattern mediated at CuI with the support of the N-heterocyclic carbene. However, a Cu–N1-ad σ-bond and a Cu···NL weak bond were observed in the structure of 2, significantly different to the bonding in 3 in which a Cu–NPh σ-bond and a Cu···N1-ad weak bond were indicated. This may suggest an initial NT (NT, terminal N atom of the azide) coordination of the azide at the Cu center followed by aryl group transfer to NT. Complex 2 may undergo further bond rearrangement of the Cu···N bonds within a pseudo-CuN3 four-membered ring as a result of the large bulk of the ligand L.
Co-reporter:ChenHui Chu;Ying Yang
Science China Chemistry 2010 Volume 53( Issue 9) pp:1970-1977
Publication Date(Web):2010 September
DOI:10.1007/s11426-010-3199-5
This paper reports the reactions of a monomeric aluminum dihydride LAlH2 (L = HC[C(Me)N(Ar)]2, Ar = 2,6-i-Pr2C6H3) with diazo, azido, and terminal alkyne compounds. The reaction of LAlH2 with N2CH(SiMe3) and N3(1-Ad) occurred through an Al-H addition to end-on nitrogen to yield respective compounds LAl[N(H)N = CH(SiMe3)]2 (1) and LAl[N(H)N=N(1-Ad)]2 (2), while the reaction of LAlH2 with PhC≡CH occurred through a stepwise deprotonation to yield LAlH(C≡CPh) (5) and LAl-(C≡CPh)2 (6), respectively. 2 further reacted by N2-release to yield LAl[NH(1-Ad)][N(H)N=N(1-Ad)] (3) and LAl[NH-(1-Ad)]2 (4) upon the increased temperature treatment. Compounds 1–6 have been fully characterized, revealing novel reactivity patterns of LAlH2 toward different substrates under the steric influence from the bulky L ligand at Al.
Co-reporter:Yan Li, Kartik Chandra Mondal, Jens Lübben, Hongping Zhu, Birger Dittrich, Indu Purushothaman, Pattiyil Parameswaran and Herbert W. Roesky
Chemical Communications 2014 - vol. 50(Issue 23) pp:NaN2989-2989
Publication Date(Web):2014/01/14
DOI:10.1039/C3CC49635J
(cAAC)Ge(GeL)2 (1) (cAAC = cyclic alkyl(amino) carbene; L = PhC(tBuN)2), a functionalized Ge3-compound was prepared. Quantum mechanical studies on 1 show a reciprocal relationship between the electronic state of the central tri-coordinated Ge atom and its reactivity towards protons, viz. tetravalent Ge(0) in terms of bonding and divalent Ge(0) in terms of reactivity. Thus the central Ge atom can be considered as having a hidden but highly reactive lone pair of electrons. However, the terminal Ge atoms can be considered as tri-coordinated divalent Ge(I) with an active lone pair of electrons.
Co-reporter:Yan Li, Kartik Chandra Mondal, Peter Stollberg, Hongping Zhu, Herbert W. Roesky, Regine Herbst-Irmer, Dietmar Stalke and Heike Fliegl
Chemical Communications 2014 - vol. 50(Issue 25) pp:NaN3358-3358
Publication Date(Web):2014/02/03
DOI:10.1039/C4CC00251B
Reaction of the monoanionic radical salt IP˙−K+ (IP = (Py)CH(=NR); Py = C5H4N, R = 2,6-iPr2C6H3; α-iminopyridine) with GeCl2(dioxane) afforded compound (IPGeCl)2 (1) which produced red blocks of IPGe: (2), when treated with KC8 in toluene. 1 is a digermylene formed via C–C coupling between two carbon-centered radicals. 2 can be considered as an analogue of a N-heterocyclic carbene, which exhibits a five-membered GeC2N2 ring with one CC double bond. 2 is formed by two-electron reduction of 1 with cleavage of the two Ge–Cl bonds and the central C–C single bond.
Co-reporter:Bin Li, Yan Li, Na Zhao, Yuefei Chen, Yujue Chen, Gang Fu, Hongping Zhu and Yuqiang Ding
Dalton Transactions 2014 - vol. 43(Issue 31) pp:NaN12108-12108
Publication Date(Web):2014/05/22
DOI:10.1039/C4DT00937A
β-Diketiminato cyclopentadienyl and ferrocenylethynyl germylenes LGeR (L = HC[C(Me)N-2,6-iPr2C6H3]2, R = Cp (1) and CCFc (2)) were prepared and utilized to synthesize the GeTe bond species. Reactions of 1, 2, and LGeCCPh (3) with an excess of Te powder proceeded in toluene under reflux successfully yielded germanetellurone L(R)GeTe (R = Cp (4), CCFc (5), and CCPh (6)). Further reaction of 4 with GeCl2·dioxane at −78 °C resulted in L(Cp)GeTe(GeCl2) (7), the first example of a germylene germanetellurone adduct. Both compounds 4 and 7 contain two isomers that are generated by the simultaneous 1,2-H- and 1,3-H-shifts over the Cp ring at the Ge atom. The reactions of L(Me)GeE with AuC6F5·SC4H8 at room temperature led to pentafluorophenyl gold(I) germanethione and germaneselone compounds L(Me)GeE(AuC6F5) (E = S (8) and Se (9)). The formation of compounds 7–9 exhibits a rare nucleophilic coordination reaction pathway by the GeE (E = S, Se, Te) bond towards the metal-containing Lewis acidic species. The structures of compounds 1, 2, and 4–9 are studied by the NMR and/or IR spectroscopy and X-ray crystallography.
Co-reporter:Yan Li, Jinjin Wang, Yile Wu, Hongping Zhu, Prinson P. Samuel and Herbert W. Roesky
Dalton Transactions 2013 - vol. 42(Issue 37) pp:NaN13722-13722
Publication Date(Web):2013/07/05
DOI:10.1039/C3DT51408K
Herein we report on the synthesis, characterization and catalytic application of metallasiloxanes of group 13–15. Reactions of R(Me)Si(OH)2 (R = N(SiMe3)-2,6-iPr2C6H3) (A) with Bi(NEt2)3, Sb(NEt2)3, Ge[N(SiMe3)2]2 and AlMe3 afforded [R(Me)SiO2BiNEt2]2 (1), [R(Me)SiO2SbOSi(OH)(Me)R]2 (2), [R(Me)SiO2]3(GeH)2 (3), and [R(Me)SiO2AlMe(THF)]2 (4), respectively. Reactions of RSi(OH)3 (B) with Bi(NEt2)3 and AlMe3 produced complexes (RSiO3Bi)4 (5) and (RSiO3)2[AlMe(THF)]3 (6). Compounds 1–6 have been characterized by IR and NMR spectroscopy, single crystal X-ray structure and elemental analysis. Each of the compounds 1, 2 and 4 features an eight-membered ring of composition Si2O4Bi2, Si2O4Sb2 and Si2O4Al2, while 3 and 6 exhibit a bicyclic structure with the respective skeletons of Si3O6Ge2 and Si2O6Al3. Compound 5 has a cubic core of Si4O12Bi4. Compounds 1–6 exhibit very good catalytic activity in the addition reaction of trimethylsilyl cyanide (TMSCN) with benzaldehyde. Compound 5 was found to be the best catalyst and its activity was probed in the reactions of TMSCN with a number of aldehydes and ketones.
Co-reporter:Xiaoping Wang, Jiancheng Li, Shimin Chen, Weiping Liu, Qingsong Ye and Hongping Zhu
Dalton Transactions 2016 - vol. 45(Issue 15) pp:NaN6717-6717
Publication Date(Web):2016/03/02
DOI:10.1039/C6DT00059B
Aryl(silyl)amino group stabilized hydridosilanediols RSiH(OH)2 (R = N(SiMe2Ph)-2,6-iPr2C6H3 (4), N(SiMe3)-2,6-iPr2C6H3 (5), and N(SiMe2Ph)-2,4,6-Me3C6H2 (6)) were prepared from the controlled hydrolysis of the related RSiHCl2 (1–3) each in the presence of aniline as the HCl acceptor. Reactions of 4 with AlMe3, AliBu3, AlH(iBu)2, and AlH3·NMe3, respectively, yielded alumino(hydrido)siloxanes [2,6-iPr2C6H3N(SiMe2Ph)Si(H)OAlMe(THF)]2 (7), [2,6-iPr2C6H3N(SiMe2Ph)Si(H)OAliBu(THF)]2 (9), [2,6-iPr2C6H3N(SiMe2Ph)Si(H)O2]3[Al(THF)]2 (10), and [2,6-iPr2C6H3N(SiMe2Ph)Si(H)OAlH(THF)]2 (11). The reaction of 5 with AlMe3 gave [2,6-iPr2C6H3N(SiMe3)Si(H)OAlMe(THF)]2 (8), a compound similar to 7. Compounds 1–11 are characterized by NMR (1H, 13C, and 29Si) and IR spectroscopy and CHN elemental analysis, of which 6 and 8–11 are further studied by X-ray crystallography. Compounds 8–9 and 11 feature cyclic structures all with the skeleton core of Si2O4Al2 while compound 10 exhibits a bicyclic structure having a core of Si3O6Al2. Melting point measurements indicated that 4–6 are thermally stable bearing the geminal SiH and SiOH groups. Compounds 8–9 and 11 are thermally stable as well with the O atom-bridged SiH and AlR (R = Me, iBu, or H) groups.
Co-reporter:Ying Yu, Jiancheng Li, Weiping Liu, Qingsong Ye and Hongping Zhu
Dalton Transactions 2016 - vol. 45(Issue 14) pp:NaN6268-6268
Publication Date(Web):2015/12/02
DOI:10.1039/C5DT03873A
Amino group combined P/Ge-based frustrated Lewis pairs (FLPs) Ph2PN(R)GeCl3 (R = 2,6-iPr2C6H3 (1), 2,4,6-Me3C6H2 (2), and C6H11 (3)) and Ph2PN(2,6-iPr2C6H3)GeMe3 (4) as well as P/Sn-based FLP Ph2PN(2,6-iPr2C6H3)SnMe3 (5) were prepared and utilized for reactions with alkyne and aldehyde molecules. Compounds 1–3 each reacted with MeO2CCCCO2Me to give zwitterionic cyclic vinyls [Ph2PN(R)GeCl3](MeO2CCCCO2Me) (6–8) and compound 1 reacted with HCCCO2Me to give the similar compound [Ph2PN(2,4,6-Me3C6H2)GeCl3](HCCCO2Me) (9). Compound 4 reacted with RCCCO2Me to afford acyclic vinyls 2,6-iPr2C6H3NP(Ph2)C(R)C(CO2Me)GeMe3 (R = CO2Me (10), H (11)) and 5 reacted with MeO2CCCCO2Me to give 2,6-iPr2C6H3NP(Ph2)C(CO2Me)C(CO2Me)SnMe3 (12). The reactions of 1 with CH3CH2CHO and 1,4-(CHO)2C6H4 were also investigated and yielded novel zwitterionic OCPNGe five-heteroatom cycles [Ph2PN(2,6-iPr2C6H3)GeCl3][CH(CH2CH3)O] (13) and [Ph2PN(2,6-iPr2C6H3)GeCl3][p-(OCH)C6H4CHO][Cl3GeN(2,6-iPr2C6H3)PPh2] (14). Compounds 1–14 were characterized by NMR (1H, 13C, and 31P) and CHN elemental analysis, of which 1, 7, and 10–14 were further studied by X-ray crystallography. The reactions of 4 (or 5) with RCCCO2Me to produce 10–12 present a novel way of obtaining the germyl (or stannyl) and iminophosphoranyl co-substituted vinyls.
Co-reporter:Yan Li, Hongping Zhu, Diego M. Andrada, Gernot Frenking and Herbert W. Roesky
Chemical Communications 2014 - vol. 50(Issue 35) pp:NaN4630-4630
Publication Date(Web):2014/03/10
DOI:10.1039/C4CC00912F
An interesting aminosilanetrithiol RSi(SH)3 (R = N(SiMe3)-2,6-iPr2C6H3) has been prepared by the reaction of lithium aminosilanetrithiolate {RSi[SLi(THF)]3}2 with MeCOOH. Theoretical calculations indicate that the LP(N) → σ*(Si–S) and LP(S) → σ*(Si–S) electron donations remarkably contribute to the stabilization of the Si(SH)3 part of the molecule. RSi(SH)3 is the first example of a stable molecule containing three SH groups attached to one element.
Co-reporter:Rui Liu, Kongtao Zhu, Xianghong Zhong, Jiancheng Li, Zhenyu Liu, Shibing Chen and Hongping Zhu
Dalton Transactions 2016 - vol. 45(Issue 42) pp:NaN17029-17029
Publication Date(Web):2016/09/22
DOI:10.1039/C6DT03216H
An amidinato-phosphino ligand ArNC(R)NH(o-Ph2PC6H4) (Ar = 2,4,6-Me3C6H2, R = Ph (1); Ar = 2,6-iPr2C6H3, R = Ph (2); Ar = 2,6-iPr2C6H3, R = tBu (3)) was prepared. The ligand reacted with CrCl3(THF)3 to yield the N,P-chelation complex [ArNHC(R)N(o-Ph2PC6H4)]CrCl3(THF) (4–6), and the ligand’s lithium salt ArNC(R)N(o-Ph2PC6H4)Li reacted with the respective CrCl3(THF)3 and CrCl2(THF)2 to give the N,N,P-chelation complexes [ArNC(R)N(o-Ph2PC6H4)]CrCl2(THF) (7–8) and {[ArNC(R)N(o-Ph2PC6H4)]Cr(μ-Cl)}2 (9–11). Complexes 1–11 were characterized by IR, NMR (for 1–3), EPR (for 4–11) spectroscopy and CHN elemental analysis, of which 3, 5, 8, and 11 were further studied by X-ray crystallography. Upon activation with an organoaluminum cocatalyst, complexes 4–6 were all catalytically active in ethylene tri-/tetramerization along with ethylene polymerization, and complexes 7–11 functioned as well but in ethylene polymerization. The correlation between the structure and the catalytic properties of the catalyst system is discussed.
Co-reporter:Bin Li, Subrata Kundu, Hongping Zhu, Helena Keil, Regine Herbst-Irmer, Dietmar Stalke, Gernot Frenking, Diego M. Andrada and Herbert W. Roesky
Chemical Communications 2017 - vol. 53(Issue 17) pp:NaN2546-2546
Publication Date(Web):2017/01/27
DOI:10.1039/C7CC00325K
The reaction of LAl: (L = HC[C(Me)N(Ar)]2, Ar = 2,6-iPr2C6H3) and cAAC:→AlX3 (X = Cl, I) (cAAC = cyclic alkyl amino carbene) results in strikingly asymmetric Al(II)–Al(II) compounds LAl(X)–Al(X)2–cAAC [X = Cl (2a); I (2b)]. In these dialuminum(II) compounds the two Al atoms bear different ligand environments. For a detailed insight into the structures, theoretical calculations were carried out.
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