Conformational behaviour of bridging diphenylphosphido ligands.
Data retrieved from the Cambridge Structural Database for crystal structures containing (µ-diphenylphosphido) metal complexes, [M(2){µ-PPh(2)}] (where M is a d-block element), have been analysed to evaluate the conformational behaviour of these species. The observed distribution of torsion angles about the P-C bonds has been compared with the potential energy surface (PES) for phenyl rotations in a representative species [(AuBr)(2){µ-PPh(2)}](-) computed using the universal force field. Good agreement was obtained between the low-energy (<8 kJ mol(-1) above the global minimum) regions of the PES and the occupied regions of the two-dimensional P-Ph rotor conformation space. Phenyl ring rotations occur by coupled, geared disrotatory and uncoupled conrotatory motions of the phenyl groups in this and other classes of PPh(2) rotors.
School of Chemistry, University of Bristol, Bristol BS8 1TS, England.
JJ
Barker
AG
Orpen