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The ferrocenylbis(methylene)phosphorane Fc-P(=CTms 2 ) 2 ( 1 ) (Fc = −C 5 H 4 FeC 5 H 5 ) can be synthesized starting from ferrocenyldichlorophosphane FcPCl 2 or ferrocenyldilithiophosphane FcPLl 2 . The X-ray structure of ( 1 ) shows some unusual structural features, which indicate considerable electronic interaction of the ferrocenyl group and the σ 3 λ 5 -phosphorane unit. As a consequence of this interaction, the rotational barrier of the methylene bonds is extraordinary low. Therefore, in contrast to other bis(methylene)phosphoranes, the endo - and exo -Tms groups are indistinguishable on the NMR time scale even at −100°C. The analogous ferrocenylbis(imino)phosphorane Fc-P(=NTms) 2 ( 9 ), can only be isolated in its dimeric form. The conditions, which are necessary for the formation of ( 9 ) from the corresponding azidophosphane Fc-P(N 3 )NTms 2 under elimination of nitrogen lead to a self addition reaction of ( 9 ). The elimination of nitrogen is facilitated by polar solvents, and electrophilic reagents. |
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