P. Wang et al., POSSIBLE HYDRIDE AND METHIDE TRANSFER-REACTION - REACTIONS OF FE(CO)(4)R- (R=H, CH3) AND W(CO)(5)R- (R=H, CH3, CL, BR, I) WITH METAL-CARBONYL CATIONS, Journal of coordination chemistry, 37(1-4), 1996, pp. 141-149
Reactions of metal carbonyl cations (M(CO)6(+), M = Mn, Re) with hydri
de-, methide- or halide-containing metal carbonyl anions (Fe(CO)(4)R-,
R = H, Me; W(CO)(5)R-, R = H, Me, Cl, Pr, I) produce products that in
dicate several mechanisms are operative. Reactions of the halo-tungste
n complexes produce neutral, solvated tungsten complexes, W(CO),(CH,CN
) and W(CO),(CH,CN), and M(CO)(5)X in a reaction that appears to be in
itiated by decomposition of W(CO)(5)X-. In contrast, the tungsten hydr
ide and methide complexes react, predominantly, by transfer of the hyd
ride or methide to a carbonyl of the cation at a much faster rate. The
iron hydride and methide complexes react by iron-based nucleophilicit
y involving a two-electron process.