Comparitive Reactivities of Two Isoelectronic Transition-Metal Hydrides with Transition-Metal Carbonyls and Alkyls

Article abstract of DOI:10.1021/ja00405a022

The two isoelectronic hydrides PPN⁺CpV(CO)3H^- (1) and -CpMo(CO)3H (2) react with a variety of metal carbonyls and alkyls.Treatment of Fe(CO)5, Cr(CO)6, (CH3C5H4)V(CO)4, CH3Re(CO)5, and (CH3CO)Re(CO)5 with 1 produces HFe(CO)4^-, HCr(CO)5^-, (CH3C5H4)V(CO)3H^-,(H)(CH3)Re(CO)4^-, and (H)(CH3CO)Re(CO)4^-, respectively, and CpV(CO)4 (3). 1 also catalyzes ligand substitution reactions in 3 and CpFe(CO)(PPh3)(COCH3).In comparison 2 reacts only with CH3Mn(CO)5 and CpMo(CO)3R (R=CH3, C2H5, CH2C6H5) producing aldehydes and the dimers 2 (4a) and 2 (5a).Reaction of 2 with ethylene produces ethane and diethyl ketone. 1 is proposed to react by an electron-transfer mechanism, whereas 2 is proposed to react by hydrogen transfer to a vacant coordination site.The relationship of the molybdenum hydride/alkyl reaction to the final step in hydroformylation (oxo process) is discussed.