78419-12-2Relevant academic research and scientific papers
Comparitive Reactivities of Two Isoelectronic Transition-Metal Hydrides with Transition-Metal Carbonyls and Alkyls
Jones, William D.,Huggins, John M.,Bergman, Robert G.
, p. 4415 - 4423 (2007/10/02)
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.
