Preferred Kinetic Migration of Methyl and Preferred Thermodynamic Migration of Phenyl in Conversion of cis-Acetylbenzoyltetracarbonylrhenate(I) to cis-Benzoylmethyltetracarbonylrhenate(I) and cis-Acetylphenyltetracarbonylrhenate(I)

Article abstract of DOI:10.1021/ja00528a033

Reaction of CH3Li with (CO)5ReCOC6H5 or reaction of C6H5Li with (CO)5ReCOCH3 produce N(CH3)4^+- (2).Thermolysis of 2 at 69 deg C produces a 98:2 mixture of N(CH3)4^+- (4) and N(CH3)4^+- (5), which equilibrate under these conditions.Reaction of 2, 4, or 5 with P(CH2CH3)3 gives N(CH3)4⁺3Re(COCH3)(COC6H5)>^- (7a).The rate of phosphine addition to 5 to give 7a is 28 times faster than the isomerization of 5 to 4.This implies that methyl migration to rhenium occurs 28-29 times faster than phenyl migration to rhenium in the five-coordinate bisacyl intermediate <(CO)3Re(COCH3)(COC6H5)>^- (6).