PUB - Publikationen an der Universität Bielefeld

Donor-acceptor interactions of Lewis bases, such as amine, phosphine, cyanic acid and phosphaalkine with various phosphinidene complexes carrying a W(CO)(5) fragment are studied by means of density functional calculations. Accordingly, the donor interactions can be divided into two categories. In terms of energy an amine binds stronger than a phosphine to a phosphinidene. the resulting Do-P bond is longer (N-P) or equal (P-P) with respect to a corresponding single bond, This tendency is also revealed in the corresponding transition metal complexes. In all cases the singlet-triplet energy separation values of the resulting donor-adducts are fairly small. A donor with a pi-system, such as HCN yields a shorter N-P bond, but the resulting donor-adduct is even less stable with respect to decomposition into a singlet PH complex and cyanic acid. Similar considerations with HCP reveal only a weak donor addition of this fragment to the parent PH complex but a facile rearrangement of the adduct to the diphosphirene transition metal complex. The diaminophosphino-PH possesses a singlet ground state, its corresponding transition metal complex reveals a fairly small singlet-triplet energy separation. It can be considered as a nucleophilic PH complex in contrast to the other homologues which reveal an electrophilic behaviour. (C) 2002 Published by Elsevier Science B.V.