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Karl Wilhelm Klinkhammer 《无机化学与普通化学杂志》2000,626(5):1217-1223
The two hypersilylcuprates LiCu2Hyp3 ( 2 ) and [Li7(OtBu)6][Cu2Hyp3] ( 3 ) (Hyp = Si(SiMe3)3) were synthesized by reactions of unsolvated lithium hypersilanide, LiHyp with hypersilylcopper and CuOtBu, respectively. Both contain the novel A‐frame trihypersilyldicuprate anion [Cu2Hyp3]–. In the former case a molecular compound is produced containing intimate ion pairs. In the latter case the cuprate anion and the unique large [Li7(OtBu)6]+ cation form a salt‐like compound, only sparingly soluble in unpolar solvents. According to NBO analyses the bonding within the trihypersilyldicuprate moiety is best described by interaction of a bridging lewis‐basic hypersilanide anion with two lewis‐acidic hypersilyl copper fragments. 相似文献
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H ? C Bond Cleavage in Ferrocene by Organylruthenium Complexes Cp*(Me3P)2RuCH2CMe3 ( 1 ) reacts at 85°C with ferrocene ( 2 ) by cleavage of one H? C bond in 2 to give CpFe[η5-C5H4Ru(PMe3)2Cp*] ( 3 ) (Cp = η5-C5H5; Cp* = η5-C5Me5) and neopentane. The ruthenium atom in 3 has a distorted tetrahedral geometry, the planar Cp ligands in the ferrocenyl fragment are eclipsed. Solutions of 3 in [D6]benzene or [D8]THF exhibit H? D exchange of the ferrocenyl protons. In the [D8]THF molecule only the α-deuterium atoms are exchanged. Reaction pathways for this exchange are discussed. 相似文献
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Komuro T Matsuo T Kawaguchi H Tatsumi K 《Journal of the American Chemical Society》2003,125(8):2070-2071
Treatment of MoCl(3)(thf)(3) with LiSC(6)H(3)-2,6-(SiMe(3))(2) (LiSAr) resulted in formation of the pi-sandwiched bis-arylthiolato complex, Mo(eta(5)-SC(6)H(3)-2,6-(SiMe(3))(2))(eta(7)-SC(6)H(3)-2,6-(SiMe(3))(2)) (1), while the analogous reaction with LiSC(6)H(3)-2-Ph-6-SiMe(3) afforded the trithiolate complex Mo(SC(6)H(3)-2-Ph-6-SiMe(3))(3) (3). The acetonitrile adduct Mo(SAr)(2)(CH(3)CN)(3) (2) was isolated from the CH(3)CN solution of 1, in which one acetonitrile is coordinated to the metal center in an eta(2)-fashion. Structures of 1, 2, and 3 have been determined by X-ray diffraction. 相似文献
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P(SiMe2)3P Li3P (produced from the elements) forms with Me2SiCl2 at 20°C in toluene the bicyclic compound P(SiMe2)3P 4 beside small amounts of ClMe2Si? P(SiMe2)2P? SiMe2Cl and traces of P4(SiMe2)6 7. 4 can be transformed into 7 by thermal treatment. With the formation of 4 the existence of a bicyclic silylphosphane is confirmed which has already been mentioned in connection with P(SiEt2)3P [1], but could not be proven until now. 相似文献
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The novel metalloid germanium cluster [Ge9(Hyp)2HypGe]– ( 1 ) was synthesized, exhibiting two different bulky groups [Hyp = Si(SiMe3)3; HypGe = Ge(SiMe3)3]. Further reaction of 1 with ZnCl2 gives the derivative [ZnGe18(Hyp)4(HypGe)2] ( 2 ) in good yield, showing that the substitution of Si(SiMe3)3 by Ge(SiMe3)3 within a metalloid Ge9R3– compound leads to a comparable reactivity. 1 and 2 are characterized by NMR spectroscopy, mass spectrometry ( 1 ) and single crystal structure analyses ( 2 ). 1 and 2 are the first metalloid germanium clusters bearing germyl groups. 相似文献
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A metal-free oxidative trifluoromethyl-thiolation of terminal alkynes using readily available CF(3)SiMe(3) and elemental sulfur at room temperature has been developed. This reaction provides an efficient and convenient method for the preparation of alkynyl trifluoromethyl sulfides bearing a wide range of functional groups. Preliminary investigation revealed that elemental sulfur instead of air acted as the oxidant. 相似文献
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Coles MP Hitchcock PB Khvostov AV Lappert MF Maron L 《Dalton transactions (Cambridge, England : 2003)》2011,40(12):3047-3052
Reduction at ambient temperature of each of the lithium benzamidinates [Li(L(1))(tmeda)] or [{Li(L(2))(OEt(2))(2)}(2)] with four equivalents of lithium metal in diethyl ether or thf furnished the brown crystalline [Li(3)(L(1))(tmeda)] (1) or [Li(thf)(4)][Li(5)(L(2))(2)(OEt(2))(2)] (2), respectively. Their structures show that in each the [N(R(1))C(R(3))NR(2)](3-) moiety has the three negative charges largely localised on each of N, N' and R = Aryl); a consequence is that the "aromatic" 2,3- and 5,6-CC bonds of R(3) approximate to being double bonds. Multinuclear NMR spectra in C(6)D(6) and C(7)D(8) show that 1 and 2 exhibit dynamic behaviour. [The following abbreviations are used: L(1) = N(SiMe(3))C(Ph)N(SiMe(3)); L(2) = N(SiMe(3))C(C(6)H(4)Me-4)N(Ph); tmeda = (Me(2)NCH(2)-)(2); thf = tetrahydrofuran.] This reduction is further supported by a DFT analysis. 相似文献
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Avent AG Antolini F Hitchcock PB Khvostov AV Lappert MF Protchenko AV 《Dalton transactions (Cambridge, England : 2003)》2006,(7):919-927
Reactions between sodium amides Na[N(SiMe3)R1] [R1 = SiMe3 (1), SiMe2Ph (2) or But (3)] and cyanoalkanes RCN (R = Ad or But) were investigated. In each case the nitrile adduct [Na{mu-N(SiMe3)2}(NCR)]2 [R = Ad (1a) or But (1b)], trans-[Na{mu-N(SiMe3)(SiMe2Ph)}(NCR)]2 [R = Ad (2a) or But (2b)], [(Na{mu-N(SiMe3)But})3(NCAd)3] (3a) or [(Na{mu-N(SiMe3)But})3(NCBut)n] [n = 3 (3b) or 2 (3c)] was isolated. The reaction of complexes 3a or 3b with benzene afforded the ketimido complex [Na{mu-N=C(Ad)(Ph)}]6.2C6H6 (4a) or [Na{mu-N=C(But)(Ph)}]6 (4b); the former was also prepared in more conventional fashion from NaPh and AdCN. The synthesis and structure of an analogue of complex 1a, [Li{mu-N(SiMe3)2}(NCAd)]2 (5a), is also presented. The compounds 1a, 1b, 2a, 2b, 3, 3b, 4a, 4b and 5a were characterised by X-ray diffraction. 相似文献
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The reaction of CuCl, LiAs(SiMe3)2 and dppb (Bis(diphenylphosphino)butane) leads to the formation of ionic cluster complexes. Depending on the reaction conditions one can isolate [Cu8As3(AsSiMe3)2(dppb)4]+[Cu{As2(SiMe3)2}{As4(SiMe3)4}]‐ ( 1 ) and [Cu8As3(AsSiMe3)2(dppb)4]+[Cu{As(SiMe3)2}2]‐ ( 2 ). The same reaction of CuCl, dppm (Bis(diphenylphosphino)methane) and LiSb(SiMe3)2 leads to the neutral cluster complex [Cu10(Sb3)2(SbSiMe3)2(dppm)6] ( 3 ). The structures of 1‐3 have been solved by X‐ray single crystal analyses. 相似文献
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Ryan A. Baldwin Hamid Rahbarnoohi Leonidas J. Jones Andrew T. McPhail Richard L. Wells Peter S. White Arnold L. Rheingold Glenn P. A. Yap 《Heteroatom Chemistry》1996,7(6):409-416
As(Si1BuMe2)3 (1) was prepared by the salt-elimination reaction between (Na/K)3As and 1BuMe2SiCl. Mixing LiAs(SiMe3)2 with Ph3SiCl (1:1) yielded As(SiMe3)2(SiPh3) (2) in a good crystalline yield. Reaction of 2 (1:1) with Et3Ga gave the expected Lewis acid-base adduct Et3Ga · As(SiMe3)2(SiPh3) (3). The 1:1 mole ratio reaction of In(SePh)3 with As(SiMe3)3 resulted in a ligand redistribution around the indium and arsenic centers to afford As(SePh)3 (4) in a low yield. The solid-state structures of 1–4 have been established by single-crystal X-ray analysis. Crystal data for 1, monoclinic space group P 21/c, with a = 11.112(2), b = 17.453(2), c = 14.199(2) Å, β = 114.89° for Z = 4; 2, orthorhombic space group P c21n, with a = 9.236(1), b = 16.612(2), c = 16.803(4) Å for Z = 4; 3, monoclinic space group P 21/c, with a = 16.799(1), b = 11.199(2), c = 19.413(3) Å, β = 112.22(1) for Z = 4; 4, trigonal space group R &3macr;, with a = 12.863(5), c = 18.96(1) Å for Z = 6. © 1996 John Wiley & Sons, Inc. 相似文献
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Herbert Schumann Jrn Winterfeld Esther C. E. Rosenthal Holger Hemling Lothar Esser 《无机化学与普通化学杂志》1995,621(1):122-130
Organometallic Compounds of the Lanthanides. 88. Monomeric Lanthanide(III) Amides: Synthesis and X-Ray Crystal Structure of [Nd{N(C6H5)(SiMe3)}3(THF)], [Li(THF)2(μ-Cl)2Nd{N(C6H3Me2-2,6)(SiMe3)}2(THF)], and [ClNd{N(C6H3-iso-Pr2-2,6)(SiMe3)} 2(THF)] A series of lanthanide(III) amides [Ln{N(C6H5) · (SiMe3)}3(THF)x] [Ln = Y ( 1 ), La ( 2 ), Nd ( 3 ), Sm ( 4 ), Eu ( 5 ), Tb ( 6 ), Er ( 8 ), Yb ( 9 ), Lu ( 10 )] could be prepared by the reaction of lanthanide trichlorides, LnCl3, with LiN(C6H5)(SiMe3). Treatment of NdCl3(THF)2 and LuCl3(THF)3 with the lithium salts of the bulky amides [N(C6H3R2-2,6)(SiMe3)]? (R = Me, iso-Pr) results in the formation of the lanthanide diamides [Li(THF)2(μ-Cl)2Nd{N(C6H3Me2-2, 6)(SiMe3)}2(THF)] ( 11 ) and [ClLn{N(C6H3-iso-Pr2-2,6)(SiMe3)} 2(THF)] [Ln = Nd ( 12 ), Lu ( 13 )], respectively. The 1H- and 13C-NMR and mass spectra of the new compounds as well as the X-ray crystal structures of the neodymium derivatives 3 , 11 and 12 are discussed. 相似文献