Basicity of Bisperhalophenyl Aurates toward Closed-Shell Metal Ions: Metallophilicity and Additional Interactions
Theoretical Chemistry Accounts, 129 (3-5):
593-602 (2011)DOI: 10.1007/s00214-011-0902-3
Abstract
The interaction of bisperhalophenyl aurates AuR2(-) (R = C6F5, C6F3Cl2, and C6Cl5) with the closed-shell Ag+, Cu+, and Tl+ ions has been studied theoretically and compared with the experimentally known X-ray diffraction crystal structures. Initially, the aurates have been fully optimized at MP2 level of theory in a D (2h) symmetry. The analysis of the basicity of the three aurates AuR2(-) (R = C6F5, C6F3Cl2 and C6Cl5) against Ag+ ions in a C (2v) symmetry has been calculated in point-by-point bsse-corrected interaction energy analysis at HF and MP2 levels of theory. Taking into account the experimental observation of additional interactions between the heterometals and C (ipso) atoms at the perhalophenyl rings or halogen atoms at the ortho position of the perhalophenyl rings, dinuclear models of the type AuR2(-)center dot center dot center dot Ag+ (R = C6Cl5, and C6F5); AuR2(-)center dot center dot center dot Cu+ (R = C6F5, and C6Cl5) and AuR2(-)center dot center dot center dot Tl+ (R = C6F5, and C6Cl5) with a C (2v) , C (2) , and C (s) symmetries have been optimized at DFT-B3LYP level. The interaction energies have been computed through bsse-corrected single point HF and MP2 calculations. The energy stabilization provided and the heterometal preference have been analyzed and compared with the experimental results.