A5011345441- Organometallic Complex Synthesis and Catalysis
- Synthesis and characterization of novel inorganic/organometallic compounds
- Coordination Chemistry and Organometallics
- Organoboron and organosilicon chemistry
- Synthetic Organic Chemistry Methods
- Organometallic Compounds Synthesis and Characterization
- Magnetism in coordination complexes
- Metal complexes synthesis and properties
- Inorganic Chemistry and Materials
- Inorganic and Organometallic Chemistry
- Asymmetric Hydrogenation and Catalysis
- Cyclopropane Reaction Mechanisms
- Ferrocene Chemistry and Applications
- Chemical Synthesis and Characterization
- Synthesis and Biological Evaluation
- Asymmetric Synthesis and Catalysis
- Catalytic Alkyne Reactions
- Chemical Reaction Mechanisms
- Metal-Catalyzed Oxygenation Mechanisms
- Organic Chemistry Cycloaddition Reactions
- Bioactive Compounds and Antitumor Agents
- Phytochemistry and biological activity of medicinal plants
- Polymer Science and PVC
- Crystal structures of chemical compounds
- Molecular Spectroscopy and Structure
Chinese University of Hong Kong
2007-2022
Chinese University of Hong Kong, Shenzhen
2016-2022
Government of Northwest Territories
2009
Shatin Hospital
2009
Chi Mei Medical Center
2005
University of Sussex
1987-1999
Low-valent metallavinylidenes :M=C/\ are scarce owing to the low stability of such species. Compound 1, prepared from [CH(Ph2P=NSiMe3)2Li(thf)] and GeCl2⋅dioxane, represents first stable bis(germavinylidene). The dimetallacyclobutanes 2 (M=Pb, Sn) were also prepared—they believed form by dimerization intermediate metallavinylidenes.
The reaction of [Ge{N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}Cl] (1) with LiBut or LiC⋮CPh in Et2O afforded substituted products [Ge(R){N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}] [R = But (2) C⋮CPh (3)], respectively. However, the one-pot 1 PhC⋮CH and BunLi lithium germinate [{(PhC⋮C)3Ge}3GeLi(Et2O)3] (4). Compound can also undergo ligand transfer LiAlH4 to give [AlH{N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}2] (5). Treatment excess NaBH4 THF germanium(II) hydride-borane adduct [Ge(BH3){N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}H]...
The reaction of germanium(<sc>i</sc>) pyridyl-1-azaallyl dimer [(RGe)<sub>2</sub>] (<bold>2</bold>) [R = {N(SiMe<sub>3</sub>)C(Ph)C(SiMe<sub>3</sub>)(C<sub>5</sub>H<sub>4</sub>N-2)}] with an excess elemental sulfur afforded unprecedented germanium analogue a dithiocarboxylic acid anhydride [{Ge(S)R}<sub>2</sub>S] (<bold>4</bold>). X-ray structures <bold>2</bold> and <bold>4</bold> have been determined.
Bis(thiophosphinoyl)methane, CH2(PPh2═S)2, and its monolithium salt [Li{(S═PPh2)2CH}(THF)(Et2O)] (1) have been used to prepare a series of low-valent group 14 metal complexes. The reaction lithium with 1 equiv MCl2 (M = Ge, Sn) in diethyl ether afforded monomeric organometal(II) chlorides [MCl{CH(PPh2═S)2}] Ge (2), Sn (3)). Treatment CH2(PPh2═S)2 equimolar M{N(SiMe3)2}2 Sn, Pb) 1,3-dimetallacyclobutanes [M{μ2-C(Ph2P═S)2}]2 (4), Pb (5)), which are believed be formed by the dimerization...
Metalations of bis(diphenylthiophosphinoyl)methane, CH2(PPh2═S)2, with equimolar BunLi or Bun2Mg in THF afforded [Li{(S═PPh2)2CH}(THF)(Et2O)] (1) and [MgC(PPh2═S)2(THF)]2 (2), respectively. Compound 1 a group 13 metal chloride MCl3 (M = Al, Ga, In) gave the methanediide complex [MCl{C(PPh2═S)2}]2 Al (3), Ga (4), In (5)). Compounds 3−5 are believed to be formed by ligand transfer reaction followed dehydrochlorination. X-ray structures 1−5 have been determined. It was found that magnesium 2...
Dimeric [Cu2(PPh2Me)4(µ,η1-CCPh)2] has been synthesized and crystallographically characterized; its photophysics together with those of other related organocopper(I) complexes, [Cu2{2-C(SiMe3)2C5H4N}2] [{Cu(C6H2Me3-2,4,6)}5] have studied Stern–Volmer quenching data the phosphorescent state pyridine complex organic halides are suggestive a charge-transfer mechanism high driving-force regime.
ADVERTISEMENT RETURN TO ISSUEPREVCommunicationNEXTSynthesis and Crystal Structure of an Unprecedented Tin(II)−Tin(II) Donor−Acceptor Complex, RN2Sn→SnCl2 [RN = CH(SiMe3)C9H6N-8]Wing-Por Leung, Wai-Him Kwok, Feng Xue, Thomas C. W. MakView Author Information Department Chemistry The Chinese University Hong Kong Shatin, New Territories, Cite this: J. Am. Chem. Soc. 1997, 119, 5, 1145–1146Publication Date (Web):February 1997Publication History Received1 August 1996Published online5 February...
This review covers the synthesis, structures, and reactivity of heavier group 14 base-stabilized heterovinylidenes featuring a >C═E: bond (E = Si, Ge, Sn, Pb). The supporting ligands used in synthesis these are mainly bulky bear electron-donating substituents which essential coordinating to metal centers for stabilization. These isolated, thermally stable analogues vinylidene have been structurally characterized. structural study bis(germavinylidene) ((Me3SiN═PPh2)2C═Ge→Ge═C(PPh2═NSiMe3)2)...
Treatment of group 14 metal dialkyl MRN2 (M = Ge or Sn) with elemental chalcogens (sulfur, selenium, tellurium) in THF afforded the corresponding chalcogenones RN2ME [RN CPh(SiMe3)C5H4N-2; M Ge; E S (4), Se (5), Te (6); Sn; (7), (8); RN CH(SiMe3)C9H6N-8, (10), (11)]. In contrast, a sulfido-bridged dimer [RN2Sn(μ-S)]2 (9) was obtained from similar reaction SnRN2 CH(SiMe3)C9H6N-8] sulfur. These have been characterized by analysis, 1H, 13C, 119Sn, 77Se, and 125Te NMR, mass spectroscopy. X-ray...
ADVERTISEMENT RETURN TO ISSUEPREVCommunicationNEXTSynthesis and Structures of Novel Low-Valent Group 14 1,3-Dimetallacyclobutanes a Mixed-Metal 1,3-Stanna−PlumbacyclobutaneWing-Por Leung, Zhong-Xia Wang, Hung-Wing Li, Qing-Chuan Yang, Thomas C. W. MakView Author Information Department Chemistry The Chinese University Hong Kong Shatin, New Territories, Kong, China Cite this: J. Am. Chem. Soc. 2001, 123, 33, 8123–8124Publication Date (Web):July 28, 2001Publication History Received27 November...
The reaction of bisgermavinylidene [(Me3SiNPPh2)2CGe→GeC(PPh2NSiMe3)2] (1) with M(CO)5(THF) ( M = Cr, W, Mo) afforded the metallagermacyclopropane [(Me3SiNPPh2)2CGeM(CO)3{M(CO)5}] [M W (2), Cr (3), Mo (4)]; in one reactions, compound 4 reacts further to give a "pincer" carbene complex [(CO)3Mo{C(Ph2PNSi Me3)2}] (5); X-ray structures compounds 2 and 5 have been determined.
Metalation of 2,6-lutidine-functionalized bis(phosphoranimines) (Me3SiNPPri2CH2)2C5H3N-2,6 (2) using MgBu2 in THF yielded the magnesium compound [Mg{(Me3SiNPPri2CH)2C5H3N-2,6}THF] (3). Further reaction 3 with 1 equiv SnCl2 afforded tin(II) [{2-{Sn{C(Pri2PNSiMe3)}}-6-{Sn{CH(Pri2PNSiMe3)}Cl}}C5H3N]2 (4). Treatment 2 Pb{N(SiMe3)2}2 lead(II) [{2-{Pb{C(Pri2PNSiMe3)}}-6-{Pb{CH(Pri2PNSiMe3)}N(SiMe3)2}}C5H3N]2 (5). X-ray structural analysis revealed that 4 and 5 consist a 1,3-dimetallacyclobutane...
A series of group 14 1,3-dimetallacyclobutanes has been synthesized and structurally characterized. The reaction the lithium compound [Li{CH(Pri2PNSiMe3)(2-Py)}] (2) with 1 equiv SnCl2 afforded tin(II) [Sn{CH(Pri2PNSiMe3)(2-Py)}Cl] (3). However, 2 MCl2 (M = Ge, Sn, Pb) in a 2:1 ratio gave corresponding metallacyclobutanes 1,3-[M{C(Pri2PNSiMe3)(2-Py)}]2 (4, M Sn; 6, Ge; 9, Pb), respectively. Reaction 3 Pb[N(SiMe3)2]2 mixed-metal cyclobutane...
The reaction of [{N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}GeCl] (1) with Na[M(η5-C5H5)(CO)3]·2DME (M = Mo, W) afforded the metallogermylenes [{N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}Ge-M(η5-C5H5)(CO)3] Mo (2), W (3)). Compounds 2 and 3 have been characterized by X-ray crystallography NMR IR spectroscopy. Structural analyses compounds are consistent presence lone-pair electrons at germanium(II) center. Ge–Mo Ge–W bond distances 2.875(1) 2.852(1) Å Ge–metal single bonds. chlorogermylene 1 was also used in...
Reactivity of the pyridyl-1-azaallyl germanium(I) dimer LGeGeL (2; L = N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)) has been investigated. Treatment 2 with 1 equiv azobenzene afforded digermahydrazine derivative [LGeNPh]2 (3). The reaction and diiron nonacarbonyl, Fe2(CO)9, novel unsymmetric complex [LGeGe(Fe(CO)4)L] (4) Lewis acid–base adduct [LGe(Fe(CO)4)]2 (5). solid-state structure 4 reveals that two centers within same molecule have different coordinating geometries. Compound can also be prepared by...
A series of heavier main Group 14 metal dialkyls MR2 [R = R1 CPh(SiMe3)(C5H4N-2), M Ge 1 or Sn 2; R R2 CH(SiMe3)(C9H6N-8), 3 Pb 4] has been synthesized by the reaction 2 equivalents appropriate lithium reagents LiR(tmen) (tmen Me2NCH2CH2NMe2) with GeCl2(diox) (diox 1,4-dioxane), SnCl2 Pb[N(SiMe3)2]2 in diethyl ether solution. Crystal structure analysis shown that compounds 1–4 are monomeric N-functionalized alkyl ligands bonded to centre a C,N-chelate fashion and geometry around is...
The novel lithium complexes [Li{N(SiMe3)C(R2)C(R1)(C5H4N-2)}]2 (R1 = H, R2 But (1b); R1 SiMe3, Ph (1c)) were prepared from the insertion of R2CN into [Li{C(SiMe3)(R1)(C5H4N-2)}]2. Similarly, Li{N(SiMe3)C(Ph)C(R)(C9H6N-2)} (R H or SiMe3) was PhCN and Li{C(SiMe3)(R)(C9H6N-2)}. X-ray data are provided for 1b, 1c, [Li{N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}(Et2O)(PhCN)] (1c'). Compounds 1b 1c dimers in solid state, whereas 1c' is monomeric.
The lithium complex [HC(PPh2NSiMe3)2Li(THF)] (2) prepared by the reaction of BunLi with bis(iminophosphorano)methane reacts GeCl2·dioxane in different stoichiometric ratios to afford [HC(PPh2NSiMe3)2GeCl] (3) and [(Me3SiNPPh2)2CGe→GeC(PPh2NSiMe3)2] (4), respectively. Bisgermavinylidene 4 can also be obtained 3 [Ge{N(SiMe3)2}2] or 2. Further Me3NO afforded [(μ-NPh2P)(Me3SiNPh2P)CGe(OSiMe3)]2 (5), direct elemental chalcogens (sulfur, selenium, tellurium) [(Me3SiNPPh2)2CGe(μ-E)]2 [E = S (6), Se...
The bisgermavinylidene [(Me3SiNPPh2)2CGe→GeC(PPh2NSiMe3)2] (1) has been used as the source of unstable germavinylidene for synthesis a series metal−germavinylidene complexes. Treatment 1 with M(PPh3)4 (M = Ni, Pd) afforded complexes [{(Me3SiNPPh2)2CGe}2Ni(PPh3)2] (2) and [{(Me3SiNPPh2)2CGe-μ2}Pd(PPh3)]2 (3), respectively. moiety from acts two-electron terminal bridging ligand, Similar reaction AgCl or AuI gave [(Me3SiNPPh2)2CGe(Ag)(Cl)]2 (5) [(Me3SiNPPh2)2CGe(Au)(I)]2 (6), result shown that...
The reaction of [MgC(PPh2═S)2(THF)]2 (1; THF = tetrahydrofuran) with 1 equiv SnCl4 in afforded a novel tin analogue allene [Sn{C(PPh2═S)2}2] (2). structure compound 2 has been characterized by X-ray crystallography and NMR spectroscopy.
The lithium complexes [Li{N(SiMe3)C(R1)C(R2)(C5H4N-2)}]2 (1a, 2a, and 3a) were each treated with MCl4 to afford the racemic [M{N(SiMe3)C(R1)C(R2)(C5H4N-2)}2Cl2] (M = Zr, R1 Ph, R2 H (1b); M But, (2b); Hf, (2c); SiMe3 (3b)). Similarly, Li{N(SiMe3)C(Ph)C(R)(C9H6N-2)} (4a 5a) afforded [Zr{N(SiMe3)C(Ph)C(R)(C9H6N-2)}2Cl2] (R (4b); R (5b)). X-ray structural analysis of 2b, 2c, 3b revealed that these have C2 octahedral geometries their chloride ligands in cis positions. Molecular orbital...
Abstract The reactivity of the lithium pyridyl‐1‐azaallyl complex [Li{N(SiMe 3 )C(Ph)C(R)(C 5 H 4 N‐2)}] 2 [R = SiMe ( 1 ) or 10 )] with group 14 metal halides has been studied under various conditions. It undergoes a salt‐elimination reaction MCl (M Ge, Sn Pb) to form [Ge{C(C N‐2)C(Ph)N(SiMe }{N(SiMe )C(Ph)C(SiMe )(C ), [M{N(SiMe N‐2)} ] [M Pb )], and N‐2)}Cl] Ge 6 7 where azaaalyl moiety acts as monodentate ligand. However, GeCl HSiCl forms )}Cl 8 [{(C N‐2)C(SiMe )C(Ph)N}(μ‐SiHCl)] 9...
The crystalline homoleptic magnesium alkyl (MgR2)∞[R = CH(SiMe3)2], derived from Mg(OC6H2But2-2,6-Me-4)2 and 2LiR, is shown by low temperature X-ray (190 K) neutron (15 diffraction to have the structure [Mg{CH(SiMe3)[SiMe2(µ-Me)]}R]∞, with MgC2C′ unit coplanar (C′ refers µ-C′H3 of a neighbouring Mg′R2 moiety), Mg-C 2.117(4) 2.105(4)Å, short Mg ⋯ C [2.535(4)Å] Mg′⋯ H [2.333(4), 2.414(5), 2.516(4)Å] contacts, bridging methyl group adopting pseudo trigonal bipyramidal arrangement [Mg C(H)3-Si:...