136823-92-2Relevant academic research and scientific papers
Intramolecular protonation and other mechanisms for substitution reactions of hydrido(thiolato)-and di(thiolato)-ruthenium(II) phosphine complexes
Jessop, Philip G.,James, Brian R.
, p. 75 - 86 (2008/10/08)
Reactions of cct-RuH(SR) (CO)2(PPh3)2 (1) (cct=cis, cis, trans) with R'SH provide cct-RuH(SR′)(CO)2(PPh3)2 (R = alkyl, aryl); based on described kinetic data, the proposed mechanism involves PPh3 loss, coordination of R′SH, intramolecular protonation of RS- by R′SH, and RSH elimination. The intramolecular protonation step circumvents a potentially slow RSH reductive elimination step. A similar mechanism is proposed for the thiol exchange reactions of cct-Ru(SR)2(CO)2(PPh3)2 (2). A corresponding dissociative mechanism is also proposed for the reaction of 1 with P(p-tolyl)3, which gives cct-RuH(SR)(CO)2(PPh3)(P(p-tolyl)3) and cct-RuH(SR)(CO)2-(P(p-tolyl)3)2. Other reactions described include the reactions of 1 with H2, CO, HCl and PPh3, and the reactions of 2 with P(p-tolyl)3 and H2. Exposure to light causes 2 to dimerize in solution.
