The carbene anions[Cp'(CO)
2Mn=C(OEt)CHR]
- ([
1]
-, Cp' =
5-MeC
5H
4; R = H, Me) react at-78
C with the
,
-unsaturated ketonesR
1(H)C=C(H)C{O}Me (
2, R
1 = H, Me, Ph) to give the
MichaeladductsCp'(CO)
2Mn=C(OEt)CH(R)CH(R
1)CH
2C{O}Me(
3) uponacidic hydrolysis at low temperature. By contrast,quenching the reaction after warming up to room temperature allows isolation of the cyclohexenone complexes
Cp'(CO)2Mn(2-CH=CHCH(R)CH(R1)CH2C{O})(5), fromwhich the corresponding substituted 2-cyclohexenones(
9)can be readily released by reaction with triphenylphosphine or carbon monoxide.