PUB - Publikationen an der Universität Bielefeld

Transient diphosphinocarbocations UP are generated either by addition of phosphenium salts to the stable [bis(diisopropylamino)phosphino](silyl)carbene or by chloride abstraction from C-phosphino-P-chloro phosphorus ylides. In contrast to their nitrogen anlogues (amidinium salts) IIN, which feature a planar 3-center-4p-electron system, calculations show that IIIp should exist as IIPb, in which one phosphorus is planar, while the other remains pyramidal. With small substituents at phosphorus, derivatives of type HIP rearrange by a 1,3-shift of a phosphorus substituent to the other phosphorus center to give C-phosphoniophosphaalkenes, When bulky substituents are present at phosphorus, derivatives IIP undergo ring closure, giving rise to the corresponding cyclic valence isomers HIP, in which the carbon atom bears a negative charge. Diphosphinocarbocations HIP can be trapped by acetonitrile giving regioselectively the corresponding [2 + 3] cycloadduct.