Synthesis and structure of {[N-[bis(diisopropylamino)phosphany]amino(phenyl)carbene}dicarbonyl-{eta(5)-methylcyclopentadienyl)manganese(0)} and experimental synthesis of {[2-bis(trimethylsilyl)methyl-3-phenyl-2H-azaphosphirene-kappa P}dicarbonyl-(eta(5)-methycyclopentadienyl)manganese(0)

Manganese carbene complexes [(MeCp)(CO)(2)Mn{C(X)Me}] 3 and 4 (3, X = OEt; 4a, X = NH2) were synthesized; complex 4a and its phenyl derivative 4b were transformed into N-lithioaminocarbene complexes [(MeCp)(CO)(2)Mn{C(N(H)Li) R}] 6a,b (6a, R = Me; 6b, R-Ph), via reaction with n-BuLi, and in turn 6a,b , in situ, via subsequent reaction with bis(diisopropylamino)chlorophosphan e (5) into metal-carbene complexes [(MeCp)(CO)(2)Mn{C(N(H)PR'(2))R}] 7a,b ( 7a, R' = (NPr2)-Pr-i, R = Me; 7b, R' = (NPr2)-Pr-i, R = Ph); the phenyl der ivative 7b has been further characterized by X-ray structure analysis. Furt hermore, generation and decomposition of the first 2H-azaphosphirene mangan ese complex is described, leading to [MeCp)(CO)(2)Mn({eta(1)-{E-(RP=PR)}}] (12) (R = CH(SiMe3)(2)).