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The addition of phosphines to the manganese allenylidene complexes Cp(CO) 2 Mn C C C(Ph)R (R = H, Ph) proceeds selectively at the C α atom to result in the α-phosphonioallenyl complexes Cp(CO) 2 Mn − –C( + PR 3 1 ) C C(Ph)R. The protonation of the latter affords the η 2 -(1,2)-phosphonioallenes Cp(CO) 2 Mn{η 2 -(1,2)-H C ( + PR 3 1 ) C C(Ph)R}, rather than the phosphoniovinylcarbenes Cp(CO) 2 Mn C( + PR 3 1 )–HC C(Ph)R. All complexes obtained are stereochemically rigid and do not isomerize into the η 2 -(2,3)-phosphonioallene isomers. |
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