149013-84-3Relevant articles and documents
Synthesis and study of the ruthenium-silence complexes (η5-C5Me5)(PR3)RuH(η 2 = SiR′2)(R = 1Pr, Cy, R′ = Me, Ph)
Champion, Brian K.,Heyn, Richard H.,Tilley, T. Don,Rheinglod, Arnold L.
, p. 5527 - 5537 (2007/10/02)
The Cp*(PR3)RuH(η2-CH2=SiR′ 2) (Cp* = η5-C5Me: 3: R = 1Pr, R′ = Me: 4: R = Cy(cyclohexyl), R′ = Me; 5: R = 1Pr, R′ = Ph; 6; E = Cy, R′ = Ph) have obtained by reaction of the appropriate ClMgCH2SIHR′2 with Cp*(PR3)RuCl. Chemical and physical for compounds are reported, Including the X-ray structure for S, which geometric parameters (Ru-Si = 1.78(2) A?; sum of angles about Si - 344°) that are consistent with significant sp2 character at silicon. Compound 5 thermally decomposes in solution to the cyclometalated product Cp*Ru[iPr2P(CMeH)CH2](H)(SiMePh 2), isolated as a 7:1 of (7a and 7b). The crystal structure of 7a was determined. Compounds 4 and 6 undergo thermolysis to the dicyclohexyl(cyclohexenyl)phosphine Cp*RuH(Cy2P(η2-C6H9)] (8), with elimination of HSiMeR2 (R = Me or Ph), A kinetic mechanistic study of the conversion of 5 to 7 indicates that the rate-limiting step is rotation of the silene to the the hydride ligand, and that the and are Compound 5 with PMe2R (R = Me, Ph) via hydride migration to the carbon and to afford Cp*(PMe2R)2RuSiMePh2 (9, R = Me; 10, R = Ph). Mechanistic show that this reaction occurs via two pathways, involving irreversible migration of hydride to the silene carbon atom and reversible of hydride to The to to Cp*(PMe3)RmH(η2-CH2=SiPh 2), which to Cp*(PMe3)RuSiMePh2. Thus, Cp*(PMe3)2RuCH2SiHPh2 (11) is not a of the reaction, as by its and study. The reaction of 5 with carbon monoxide in a manner via both to Cp*(PPr3)(CO)RuCH2SiHPh2 (12) and Cp*(PiPr3)(CO)RuCH2SiMePh2 (13). The of 5 with can be explained by a mechanism involving two hydride-migration pathways, (14) and (via of Cp*(PiPr3)RuCH2SiHPh2), and (15, via of Cp*(PiPr3)RuSiMePh2). Compound 15 may be obtained by hydrogenation of 7. The of 5 with COS lead to cleavage to react of the C-S bond and formation of Cp (P1Pr3)(CO)RuSSiMePh2 (16). Electrphilics Me3SnCl and HCl appear to react with 5 via initial electrephailic attack at ruthenium, but different migration process are to observed occur. Thus, the reaction with Me3SnCl principally Cp*(PPr3)RuCl and Me3SnCH2SiHPh2 The reaction with HCl produces ClSiMePh2, 7, Cp*(PiPr3)EuCl, 14. Mechanisms for the are above reactions are discussed.
