First Structural Characterization of Silanedithiol and Its Application toward the Synthesis of Silanedithiolato Complexes

In this paper, we report the synthesis and the structural characterization of stable examples of silanedithiol [Tbt(Mes)Si(SH) 2 ( 1 )], hydroxysilanethiol [Tbt(Mes)Si(OH)(SH) ( 3 )], and hydroxysilaneselenol [Tbt(Mes)Si(OH)(SeH) ( 7 )], which are kinetically stabilized by an effective combination of steric protection groups, Tbt (2,4,6‐tris[bis(trimethylsilyl)methyl]phenyl) and Mes (2,4,6‐trimethylphenyl). Silanedichalcogenols 1 , 3 , and 7 are suggested to exist as a monomer without any intermolecular contact such as hydrogen bonds both in the solid state and in solution as judged by X‐ray structural analysis and IR spectroscopy. Treatment of 1 with 2 equiv. of butyllithium resulted in the quantitative formation of the corresponding dilithium silanedithiolate, Tbt(Mes)Si(SLi) 2 ( 8 ), the generation of which was confirmed by a trapping experiment using MeI. Furthermore, the addition of cis ‐[MCl 2 (PPh 3 ) 2 ] (M = Pd, Pt) to a THF solution of 8 afforded the corresponding silanedithiolato complexes, [Tbt(Mes)Si(μ‐S) 2 M(PPh 3 ) 2 ] ( 9a : M = Pd; 9b : M = Pt), respectively. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)