Lm. Toomey et Jd. Atwood, ABSTRACTION OF METHYL FROM NEUTRAL FISCHER-TYPE CARBENE COMPLEXES - ANEW SITE FOR NUCLEOPHILIC-ATTACK, Organometallics, 16(3), 1997, pp. 490-493
Reactions of Fischer-type carbene complexes, M(CO)(5)(C(OMe)Ph) (M = C
r, W), with metal carbonyl anions (M'(-) = CpFe(CO)(2)(-), Re(CO)(5)(-
), Mn(CO)(4)PPh(3)(-) Co(CO)(3)PPh(3)(-), CpCr(CO)(3)(-), CpMo(CO)(3)
(-)) result in demethylation of the carbene complexes. The products ar
e M(CO)(5)C(O)Ph(-) and M'-Me, characterized by infrared and MMR spect
roscopy. A slower rate for reaction with W(CO)(5)(C(OEt)Ph) in compari
son to the methyl analogue is consistent with nucleophilic attack of t
he metal carbonyl anion on the methyl of the methoxy group of the carb
ene. This is a new type of nucleophilic attack on a Fischer-type carbe
ne.