The transient electrophilic phosphinidene complex PhPW(CO)(5) reacts in the
presence of CuCl at room temperature with phospholene 2 and phospholes 4a-
c to give the corresponding W(CO)(5) complexed products 3 and 5a-c. The int
ermediate phosphoranylidene phosphine complexes, formed, from the addition
of PhPW(CO)(5) to the phosphorus atom of the substrates, are characterized
by NMR spectroscopy and by a single crystal X-ray structure determination f
or the one generated from phospholene 2. This intermediate 8 is a CuCl-comp
lexed dimer, which speculatively results from dissociating the phosphole-Cu
Cl tetramer on insertion of PhPW(CO)(5) into the P-Cu bonds. Reacting PhPW(
CO)(5) with phospholene 2 at 110 degreesC in the absence of CuCl gives besi
des the W(CO)(5)-complexed phospholene 3 also a bisphospholene-W(CO)(4) com
plex 13. The formation of 13 is attributed to a ligand exchange reaction in
the intermediate phosphinidene-phospholene adduct. (C) 2001 Elsevier Scien
ce B.V. All rights reserved.