Unique intramolecular exchange between H of SiHPh2 and SAr in [RhH(SiHPh2)(SAr)(PMe3)3]

Transformation of Thiolatogold(I) to an Au Complex with an (Arylthio)silyl Ligand. Use of an (Aminosilyl)boronic Ester as a Silylene Precursor

“…(2.228(1) Å). 13 The Au−P bond of complex 2 (2.274(2) Å) is shorter than the bond of complex 3 (2.362(2) Å) because of the larger trans influence of the silyl ligand in comparison to the thiolate ligand. NMR spectra of the complexes agree with the structures by X-ray crystallography.…”

“…The Au–Si bond distance of complex 3 (2.345(2) Å) is similar to that of [Au­(SiPh 2 Cl)­(PCy 3 )] (2.343(4) Å) and is within the range of those of Au­(I) complexes with silyl ligands (2.25–2.58 Å) . The Si–S bond of 3 (2.187(3) Å) is shorter than the corresponding bond of fac -[RhH 2 (SiPh 2 (SPh))­(PMe 3 ) 3 ] (2.228(1) Å) . The Au–P bond of complex 2 (2.274(2) Å) is shorter than the bond of complex 3 (2.362(2) Å) because of the larger trans influence of the silyl ligand in comparison to the thiolate ligand.…”

MOLECULAR STRUCTURE OF ORGANOSILICON COMPOUNDS WITH Si - Ru, Si - Rh and Si - Pd BONDS

“…The shortest Rh -Si bond distances of 2.229 and 2.293 A (for two independent molecules) were obtained for complex 59 [R 3 Si=(MeO) 3 Si, X=PhS] bearing electron-acceptor methoxy groups at the silicon atom. Complexes 60 (R 3 Si=Ph 2 ClSi [71], Ph 2 (PhS)Si [73,74] are characterized by facial arrangement of three Me 3 P ligands and mutually cis position of two hydrides. The Rh -Si distance in chlorodiphenylsilyl complex (2.314 Ä) is slightly shorter than in diphenyl(phenylthio)silyl one (2.342 A).…”

Chemistry of Compounds with Silicon–Sulphur, Silicon–Selenium and Silicon–Tellurium Bonds

“…Since the silyl group in 3 is trans to the thio group and the isomerization is intramolecular, it is suggested that cis trans isomerization occurs prior to transfer (equation 11) 19 …”

“…At 85°C, both compounds reduce terminal alkenyl bromides to the alkene or cycloalkane. With (Me 3 Si) 2 Si(Me)SH, the thiyl radical reduces terminal alkyl bromides to the alkene and likewise isomerizes to a silthiane (equation 19), while allylSSi(SiMe 3 ) 3 is less efficient than tin-substituted propenes in radical allylations 32 . Reacting Me 2 SiCl 2 with H 2 S at 78°C gives the silane dithiol as an unstable oil which shows S H stretching at 2500 cm 1 .…”