27599-25-3Relevant articles and documents
Exceedingly Facile Ph-X Activation (X=Cl, Br, I) with Ruthenium(II): Arresting Kinetics, Autocatalysis, and Mechanisms
Miloserdov, Fedor M.,McKay, David,Mu?oz, Bianca K.,Samouei, Hamidreza,MacGregor, Stuart A.,Grushin, Vladimir V.
, p. 8466 - 8470 (2015/11/27)
[(Ph3P)3Ru(L)(H)2] (where L=H2 (1) in the presence of styrene, Ph3P (3), and N2 (4)) cleave the Ph-X bond (X=Cl, Br, I) at RT to give [(Ph3P)3RuH(X)] (2) and PhH. A combined experimental and DFT study points to [(Ph3P)3Ru(H)2] as the reactive species generated upon spontaneous loss of L from 3 and 4. The reaction of 3 with excess PhI displays striking kinetics which initially appears zeroth order in Ru. However mechanistic studies reveal that this is due to autocatalysis comprising two factors: 1) complex 2, originating from the initial PhI activation with 3, is roughly as reactive toward PhI as 3 itself; and 2) the Ph-I bond cleavage with the just-produced 2 gives rise to [(Ph3P)2RuI2], which quickly comproportionates with the still-present 3 to recover 2. Both the initial and onward activation reactions involve PPh3 dissociation, PhI coordination to Ru through I, rearrangement to a η2-PhI intermediate, and Ph-I oxidative addition.
C-C bond formation via C-H bond activation using an in situ-generated ruthenium catalyst
Martinez, Remi,Simon, Marc-Olivier,Chevalier, Reynald,Pautigny, Cyrielle,Genet, Jean-Pierre,Darses, Sylvain
, p. 7887 - 7895 (2009/10/17)
We report here our full results concerning the possibility of generatingin situ from a stable and readily available ruthenium(II) source a high ly active ruthenium catalyst for C-H bond activation. The versatility ofthis catalytic system has been demonstrated, as it offers the possibili ty of modifying the electronic and steric properties of the catalyst by fine-tuning of the ligands, allowing functionalization of various substrates. Aromatic ketones and imines could be easily functionalized by the reaction with either vinylsilanes or styrenes, depending on the electronic and steric nature of the ligand. Moreover, variable-temperature NMR experiments and the isolation of a ruthenium intermediate complex provided some insights into the generation of the active catalytic ruthenium species in this reaction.
Roles of Neutral and Anionic Ruthenium Polyhydrides in the Catalytic Hydrogenation of Ketones and Arenes
Linn, Donald E.,Halpern, Jack
, p. 2969 - 2974 (2007/10/02)
fac-- (1) and (3) have been shown to coexist through the equilibrium 1 + ROH 3 + RO-, for which Keq ca. 0.13 for cyclohexanol in THF.The following reactions have been characterized: (1) 3 +
