1,4-addition of a phosphinidene complex to Cisoid 1,3-dienes

The first genuine 1,4-additions of the terminal phosphinidene complex PhPW( CO)(5) (2) to 1,3-dienes 3 are reported. Two of the 1,4-adducts, 15 and 17, were characterised by X-ray crystal structure determinations. A cisoid con formation, but not coplanarity, of 3 appears to be a prerequisite for the o ccurrence of a 1,4-addition. The reaction of 2 with the sterically hindered 3B yields 66.5% of the 1,4-addition product 13, the highest percentage of 1,4-addition thus far observed for the reaction of an electrophilic species with a 1,3-diene. The product composition is almost independent of the tem perature, implying that the usual preference for the 1,2-mode is mainly ent ropy controlled. Steric factors appear to be the main cause of the higher t endency towards 1,4-addition of phosphinidines as compared to carbenes. (C) 1999 Elsevier Science Ltd. All rights reserved.