Zur Insertion von Decamethylsilicocen in Nickel- und Gold-Chlor-Bindungen

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• 作者：Theil ; Martin ; Jutzi ; Peter ; Neumann ; Beate ; Stammler ; Anja ; Stammler ; Hans-Georg
• 关键词：Decamethylsilicocene ; Insertion reactions ; Cp* substituent ; Silyl-transition metal complexes ; π ; -Interaction
• 刊名：Journal of Organometallic Chemistry
• 出版年：2002
• 出版时间：November 15, 2002
• 年：2002
• 卷：662
• 期：1-2
• 页码：34-42
• 全文大小：221 K

文摘

The reaction of decamethylsilicocene (1) with CpNiCl(PPh₃) (4) leads to the silylnickel complex [Cp*₂(Cl)Si]NiCp (5), in which an intramolecular π-interaction between a σ-bound Cp* substituent and the nickel atom is observed, in the solid state as well as in solution. Reaction of 1 with gold(I) chloride complexes ClAuL results in the formation of the insertion products [Cp*₂(Cl)Si]AuL (L=Ph₃P (6), ^tBuNC (7), C₅H₅N (8), THT (9)). The thermolabile and air-sensitive silylgold complex {[Cp*₂(Cl)Si]Au}_n (10) is formed in the reaction of 1 with ClAu(CO). Proposals for the structure of 10 are given on the basis of NMR investigations and of crystal structure information for 5 and 6. Addition of donor molecules L to 10 yields the complexes 6–9, [Cp*₂(Cl)Si]AuPMe₃ (11) and [Cp*₂(Cl)Si]AuPEt₃ (12). A π-interaction between a Si-bound Cp* substituent and the central atom is observed also in the silylgold complexes 6–12. Most compounds are characterized by NMR spectroscopic and mass spectrometric data, compounds 5 and 6 also by X-ray crystallography. Earlier structure assignments for 7, 8 and 10 have to be corrected.