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

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.