Reaction of a Complexed Phosphinidene with 2,4,6-Tri-tert-butyl-1,3,5-triphosphabenzene

摘要

The terminal phosphinidene complex PhPW(CO)_5 reacts with 2,4,6,-tritert-butyl-1,3,5-triphosphabenzene to give two unexpected multicyclic organophosphorus compounds.One of them results from an initial 1,2-addition,followed by an intramolecular rearrangement.B3LYP/6-31G~* calculations on simplified parent systems suggest that the reaction follows a umique concerted reaction pathway.The second,and major,product is a tetraphosphaquadricyclane derivative,which presumably results from an intramolecular [2+2] cycloaddition of an intermediate tetraphosphanorbornadiene complex.Single-crystal X-ray structures are presented for both products.