Journal article
Ferrocenylbis(ylene)phosphoranes.



Publication Details
Authors:
Pietschnig, R.; Nieger, M.; Niecke, E.; Airola, K.
Publisher:
ElsevierDO - 10.1016/S0022-328X(97)00066-1
Publication year:
1997
Journal:
Journal of Organometallic Chemistry
Pages range:
237-242
Volume number:
541
Start page:
237
End page:
242
ISSN:
0022-328X

Abstract
The ferrocenylbis(methylene)phosphorane FcP(:CTms2)2 (1) (Fc = C5H4FeC5H5, Tms = SiMe3) can be synthesized starting from FcPCl2 or FcPLi2. The x-ray structure of (1) shows some unusual structural features, which indicate considerable electronic interaction of the ferrocenyl group and the σ3λ5-phosphorane unit. As a consequence of this interaction, the rotational barrier of the methylene bonds in 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°. The analogous ferrocenylbis(imino)phosphorane FcP(:NTms)2 (9), can only be isolated in its dimeric form. The conditions, which are necessary for the formation of (9) from the corresponding azidophosphine FcP(N3)(NTms2) under elimination of N lead to a self addn. reaction of (9). The elimination of N is facilitated by polar solvents, and electrophilic reagents. [on SciFinder(R)]


Keywords
azidophosphine ferrocenyl prepn elimination nitrogen, crystal structure ferrocenyl bisdisilylmethylene phosphorane, ferrocenyl bisylene phosphorane prepn crystal structure, iminophosphorane ferrocenyl prepn, mol structure ferrocenyl bisdisilylmethylene phosphorane


Authors/Editors

Last updated on 2019-25-07 at 16:00