Interplay between Gold(I)-Ligand Bond Components and Hydrogen Bonding: A Combined Experimental/Computational Study

The influence of weak interactions on the donation/back-donation bond components in the complex [(NHC)Au( SeU )] + (NHC = N-heterocyclic carbene; SeU = selenourea) has been studied by coupling experimental and theoretical techniques. In particular, NMR 1 H and pulsed-field gradient spin-echo titrations allowed us to characterize the hydrogen bond (HB) between the -NH 2 moieties of SeU and the anions PF 6 - and ClO 4 - , whereas 77 Se NMR spectroscopy allowed us to characterize the Au-Se bond. Theoretically, the Au-Se and Au-C orbital interactions have been decomposed using the natural orbital for the chemical valence framework and the bond components quantified through the charge displacement analysis. This methodology provides the quantification of the Dewar-Chatt-Duncanson (DCD) components for the Au-C and Au-Se bonds in the absence and presence of the second-sphere HB. The results presented here show that the anion has a dual mode action: it modifies the conformation of the cation by ion pairing (and this already influences the DCD components) and it induces new polarization effects that depend on the relative anion/cation relative orientation. The perchlorate polarizes SeU , enhancing the Se → Au σ donation and the Au → C back-donation and depressing the C → Au σ donation. On the contrary, the hexafluorophosphate depresses both the Se → Au and C → Au σ donations.