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

Abstract

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‐[MCl2(PPh3)2] (M = Pd, Pt) to a THF solution of 8 afforded the corresponding silanedithiolato complexes, [Tbt(Mes)Si(μ‐S)2M(PPh3)2] (9a: M = Pd; 9b: M = Pt), respectively. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Reactivity of the bis(silyl) palladium(II) complex toward organic isothiocyanates

“…1 shows the molecular structure of cis-[Pd(S 2 SiPh 2 ) (dmpe)] (2), which shows a slightly distorted square-planar coordination, consisting of two PMe 2 groups and two bridging sulfide (meS) ligands that are linked to the SiPh 2 . The PdeS bond lengths (2.378(6) and 2.391(6) Å) in 2 are close to those (2.362 (1) [40]. These data indicate that the dithiolatoePd (II) complexes are less symmetric (different MeS bond lengths) than the Pt(II) complexes having a bridged silane group, reflecting more distorted metallacyclobutane rings containing diphenylsilyl group in the former than those in the latter ones.…”

Syntheses and structures of overcrowded silanedichalcogenols and their applications to the syntheses of silanedichalcogenolato complexes

“…The silanedithiol 1a was considered to be applicable toward the development of a new synthetic strategy for silanedithiolato transition metal complexes. The addition of cis-[MCl 2 (PPh 3 ) 2 ] (M = Pd, Pt) to the THF solution of silanedithiolate 10a resulted in the almost quantitative formation of the corresponding silanedithiolato complexes of palladium and platinum, [Tbt(Mes)Si(l-S) 2 M(PPh 3 ) 2 ] (16: M = Pd, 17a: M = Pt), respectively, as air-and moisture-stable yellow crystals (Scheme 7) [16]. Both of the central four-membered rings in 16 and 17a consisting of Si, two S, and Pd or Pt atoms have puckered structures (Figs.…”

“…doi: 10.1016/j.jorganchem.2008.11.001 complexes of group 10 transition metals by taking advantage of the isolated silanedichalcogenols. Portions of this work were communicated as preliminary reports [16,17]. In this paper, we will report the detailed synthesis, structures, and properties of the newly isolated silanedichalcogenols and their applications to the synthesis of novel four-membered-ring compounds consisting of one silicon and two chalcogen atoms together with a heavier group 15 atom [Sb, Bi] or a transition metal [Pd, Pt, Ru].…”

A Bulky Silylene Generated under Mild Conditions: Its Application to the Synthesis of Organosilicon Compounds

“…53 Compounds 21a and 21b could not be isolated due to their high reactivity to H 2 O giving the corresponding silanedithiol 22a and hydroxysilaneselenol 22b, respectively. The formation of 22b can be explained in terms of further hydrolysis of the intermediary silanediselenol Tbt(Mes)Si(SeH) 2 .…”