Synthesis and structural characterization of silanethiolato complexes having tert-butyldimethylsilyl and trimethylsilyl groups

Treatment of cyclotrisilathiane (Me₂SiS)₃ with 3 equiv. of RLi (R = Me, Bu^t) in hexane-Et₂O afforded the lithium silanethiolates LiSSiMe₂R, and the tmeda adduct [(tmeda)LiSSiMe₂Bu^t]₂ 1(tmeda = N,N,N′,N′-tetramethylethylenediamine) was isolated in the case of R = Bu^t. Reaction of Fe(CH₃CN)₂(CF ₃SO₃)₂, CoCl₂, and [Cu(CH ₃CN)₄](PF₆) with 1 gave rise to the silanethiolato complexes M(SSiMe₂Bu^t)₂(tmeda) (M = Fe 2, Co 3), and [Cu(SSiMe₂Bu^t)]₄ 4, respectively. Complexes (C₅H₅)₂Ti(SSiMe ₂R)₂ (R = Me 5, Bu^t 6) and Ni(SSiMe ²R)₂(dppe) [R = Me 7, Bu^t 8; dppe = 1,2-bis(diphenylphosphino)ethane] were prepared from treatments of (C ₅H₅)₂TiCl₂ and NiCl ₂(dppe) with the corresponding lithium silanethiolates. Complex 7 readily reacted with (C₅H₅)TiCl₃ to produce the Ti-Ni heterobimetallic compound (C₅H₅)TiCl(μ-S) ₂Ni(dppe) 9, in which silicon-sulfur bond cleavage took place. Characterization of all compounds through spectroscopic techniques and elemental analyses are also described. X-Ray structural data for compounds 1 and 3-9 are reported.