Synthesis of the first stable Fischer-type carbene metal complex with a COP structural motive of the carbene ligand

Fischer-type (phenyl)carbene pentacarbonyltungsten complexes, which have an organo phosphorus moiety bonded to oxygen (5, 8) or to nitrogen (10a,b), are synthesized by reaction of the OLi and NLi precursor carbene complexes with either bis(diisopropylamino)chlorophosphane (5) and/or [bis(trimethylsilyl)methylene]chlorophosphane (8, 10a,b) via lithiumchloride elimination; whereas the bulky substituted complex 5 decomposed in solution under formation of bis(diisopropylamino)-chlorophosphaneoxide via an unknown reaction pathway, complex 8 was stable at ambient temperature; complexes 10a,b slowly rearranged in solution to the 2H-azaphosphirene complex 11; the complexes 8 and 10a,b were unambiguously confirmed by NMR spectroscopy.