Synthesis and Spectral Properties of Novel Si-Ru-Ru-Si-C6H4 Polymers

Abstract

Dehydrogenative coupling reactions of bis(hydrosilyl)benzenes with [Ru3(CO)12] afford moderate yields of the polymers [-SiRR′-Ru(CO)4-Ru(CO)4-SiRR′-C6H4-]n which exhibit large solvent-dependent change of the UV-VIS spectra. The absorption maximum of the polymer is markedly red-shifted, compared with monomeric complex [PhMe2SiRu(CO)4Ru(CO)4SiMe2Ph].

Reactions of Hydrosilanes with Transition Metal Complexes and Characterization of the Products

“…In the simplest case, Ru 3 (CO) 12 reacted with PhMe 2 SiH to give [PhMe 2 SiRu(CO) 4 ] 2 , 3-140, and with p-HMe 2 SiC 6 H 4 -SiMe 2 H to give the polymer -[Me 2 SiRu(CO) 4 Ru(CO) 4 -SiMe 2 ] n -, 3-141. 216 A more complicated sequence occurred when Ru 3 (CO) 10 (dppm) (which contains a triangular Ru 3 core with dppm displacing a CO ligand at each of two Ru centers) reacted with the secondary silane, (p-Tol) 2 SiH 2 . 99 In the first step (reaction conducted at 40°C), (p-Tol) 2 Si displaces the Ru(CO) 4 unit, giving 2-42a.…”

“… 29 Publication provides only the X-ray structure. Two molecules in the asymmetric unit. 371 , 216 30 Hydrogens were included in the model at geometrically calculated positions but were not refined 91 31 Precise location of the 6 H’s could not be confirmed; they were presumed to be in axial positions of a tricapped trigonal prism 172 …”

“… 156 Complex also generated from DSiMe 2 Ph 157 Additional derivatives, R = Me, R′ = Ph, Ph = 1,4-C 6 H 4 ; R = R′ = Me, Ph = 1,4-C 6 H 4 158 M w = 15 000; P D = 2.5 …”

“… 157 Additional derivatives, R = Me, R′ = Ph, Ph = 1,4-C 6 H 4 ; R = R′ = Me, Ph = 1,4-C 6 H 4 158 M w = 15 000; P D = 2.5 159 The 29 Si(INEPT){ 1 H OMe }{ 31 P} spectrum shows a nonet …”

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

“…The SiRuRuSi unit of complex PhMe 2 SiRu(CO)4Ru(CO)4SiMe 2 Ph [26] has also the linear geometry. Although each Ru atom is coordinated by four carbonyl ligands, disorder effect provides eight equivalent CO positions.…”