55102-19-7Relevant articles and documents
Olefins isomerization by hydride-complexes of ruthenium
Yue, Chuan Jun,Liu, Ying,He, Ren
, p. 17 - 23 (2006)
Several complexes containing the Ru-H bond were synthesized according to previous reports: RuH(NO)(PPh3)3(I) (1), RuHCl(PPh3)3(s)(II) (2), RuHCl(CO)(PPh3)3(II) (3), RuH(CH3COO)(P
Towarnicky, J. M.,Schram, E. P.
, p. 55 - 60 (1980)
Coordination, agostic stabilization, and C-H bond activation of N-alkyl heterocyclic carbenes by coordinatively unsaturated ruthenium hydride chloride complexes
Burling, Suzanne,Mas-Marza, Elena,Valpuesta, Jose E. V.,Mahon, Mary F.,Whittlesey, Michael K.
, p. 6676 - 6686 (2009)
The products formed upon reaction of Ru(PPh3)3HCl and [Ru(PiPr3)2HCl]2 with the N-heterocyclic carbenes l,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (I iPr2Me2,1) and 1,3-dieth
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.
