Rj. Deeth, THE TRANS INFLUENCE IN [RH(PH3)3CL] - A DENSITY-FUNCTIONAL THEORY STUDY, Journal of the Chemical Society. Dalton transactions, (24), 1993, pp. 3711-3713
Optimised geometries computed using the local density approximation (L
DA) of density functional theory (DFT) have been obtained for the Wilk
inson's catalyst model complex [Rh(PH3)3Cl]. The LDA method accurately
predicts the 0.09 angstrom shortening of the Rh-P(trans) distance rel
ative to Rh-P(cis) although the Rh-Cl contact is about 0.05 angstrom t
oo short. These geometrical data are significantly better than single
determinant Hartree-Fock (HF) results. In contrast, the Mulliken charg
e density analyses are very similar and give comparable descriptions o
f the bonding although small differences in the predicted d-orbital se
quences suggest that the LDA method describes a stronger in-plane pi-a
cceptor interaction than does HF theory.