Reactions of anionic transition metal carbonyl hydrides with electrophilic metal carbonyls: Nucleophilic addition (hydride transfer) vs. electron transfer mechanisms
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The relative reactivity of anionic transition metal carbonyl hydrides towards hydride transfer to monomeric metal carbonyls is consistent with an ionic route, generating, in the best-matched cases of electrophilic carbonyls (highest fCO or average v(CO)) and most nucleophilic hydrides (such as HW(CO)4P(OMe)3-), metal formyls as sole product. With the metal carbonyl dimers Co2(CO)8, [(η5-C5H5)M(CO)3]2 (M = Mo, W), and Mn2(CO)10 reductive cleavage to the respective anions occurs at rates which correlate with the nucleophilicity of the metal hydride, without observation of intermediate formyls. No reaction occurs with Re2(CO)10 or [(η5-C5H5)Fe(CO)2]2. © 1990.
author list (cited authors)
Darensbourg, M. Y., Ash, C. E., Arndt, L. W., Janzen, C. P., Youngdahl, K. A., & Park, Y. K.