220628-24-0Relevant academic research and scientific papers
C-(halide) oxidative addition routes to ruthenium carbenes
Olivan, Montserrat,Caulton, Kenneth G.
, p. 566 - 570 (2008/10/08)
Ru(H)2(H2)2L2 (L = PCy3) reacts with CHRCl2 (R = H, Ph) to give Ru(CHR)Cl2L2 and H2. Using Cl2C=CH2 as the gem-dihalide gives Ru(CHCH3)Cl2L2, due to hydrogenation of the C=C bond of the presumed vinylidene primary product by released H2. Released H2 also reacts with Ru(CHR)Cl2L2 (R = H, Ph) to give H2CR, HCl and RuHCl(H2)L2. This undesirability of H2 as a coproduct can be diminished by using Ru(H)2(N2)2L2 as the reagent, giving Ru(CHR)Cl2L2 and 1H2 and 2N2 as products. Reaction of Ru(H)2(N2)2L2 with Cl2CHEt gives RuCl2(CHEt)L2 and RuHCl(N2)L2, the latter apparently by competitive β-H migration from an intermediate RuHCl(CHClEt)L2 species. When Ru(H)2(N2)2L2 is reacted with the monochloride PhCH2Cl, the primary product RuCl(CH2Ph)(H2)L2 slowly (hours) evolves further to give RuHCl(N2)L2 and PhCH3. Reaction of Ru(H)2(N2)2L2 with C6F6, BrHC=CHPh, and CH3I give RuHX(N2)L2 (X = F, Br, I, respectively). The N2 ligand in RuHCl(N2)L2 can be displaced by H2 and by CO, while H2 converts RuHF(N2)L2 to Ru(H)2(H2)2L2 and HF.
