Mechanisms of group transfer in anionic transition metal hydrides and alkyls

Abstract

Studies of intermolecular hydride transfer from coordinatively saturated HM(CO)4L (M - Cr, W; L - CO, PR3) conclude the M-H functional group to be isolated and the gp 6 metal center to be inaccessible to entering substrates. In contrast the analogous HFe(CO)3L show a metal-based, rather than hydride-based, nucleophilicity. Hydride transfer reactions of HW(CO)5 are compared with the methyl analogues in MeW(CO)5. The latter are considerably more sluggish in reactions with various organic substrates (RX, RC(0)C1, RC(O)H) and disuplay characteristics of Me. radical intermediates. © 1988 IUPAC