Effect of phosphine substituents in gold(I) complexes: a theoretical study of MeAuPR3, R = H, Me, Ph

Abstract

Electronic structure investigations on triphenylphosphine (PPh3) ligated gold clusters are commonly carried out with model phosphine ligands. To explore the validity and the limitations of this approach, we have studied the effects of phosphine substituents in a series of gold(1) compounds: MeAuPR3, R = H, Me, Ph. We used the recently developed scalar-relativistic version of the linear combination of Gaussian-type orbitals (LCGTO) local density functional (LDF) method which allows an all-electron treatment of all systems under study. For structural properties the PH3 ligand provides a satisfactory model of the full PPh3 ligand. But the trimethylphosphine ligated models have to be employed if good agreement is desired for energy properties and for the dipole moment.

Polymer-Supported Carbene Complexes of Palladium: Well-Defined, Air-Stable, Recyclable Catalysts for the Heck Reaction

“…It was shown in previous studies that PMe 3 dissociation energies compare much better with those for phosphine ligands commonly used in catalysis (i.e., PPh 3 , PCy 3 ) than with PH 3 dissociation energies. [12,27] The The calculations show, in accord with earlier studies on other transition metals [12,27] and in agreement with more qualitative considerations, [11] that PMe 3 is considerably more tightly bound to palladium(ii) than PH 3 . Still, the phosphine Scheme 1.…”

Ab initio Study on Luminescence and Aurophilicity of a Dinuclear [(AuPH3)2(i‐mnt)] Complex (i‐mnt = isomer‐Malononitriledithiolate)

“…A similar model was applied in our previous work [28] by using dpm to stand for dmpm, dppm and dcpm in the [Au 2 [45] have proved that PH 3 provided a satisfactory model for PMe 3 or PPh 3 for the structural properties of Au I complexes. Bruce [22] and other researchers [26,46,47] have successfully used such a kind of model in their theoretical studies on the related topics of (phosphane)Au I complexes.…”

Density functional study of aurophilic interaction in Cl(AuPH3) and in its dimerization

“…For computational efficiency, it was replaced by the phosphine group, OPH 3 . This substitution has been found to have little influence on the XOAu and AuOP bond lengths [7]. For the bridged monomer Cl(AuPH 3 ) 2 ϩ (referred to as "A-frames" below), C 2v symmetry is assumed.…”