New light on an old debate: does the RCN-PtCl bond include any back-donation? RCN←PtCl backbonding vs. the IR ν blue-shift dichotomy in organonitriles-platinum(ii) complexes. A thorough density functional theory - energy decomposition analysis study.

For a series of organonitrile [RCN (R = Me, CF, Ph, CHPh, CFPh)] ligands, the nature of the N-Pt bond in the related cis-/trans-(RCN)PtCl complexes has been computationally investigated by Density Functional Theory. A fragment based bond analysis has been performed in the canonical Kohn-Sham molecular orbitals framework, and it has been ultimately assessed that this bond is characterized both by N→Pt σ and by N←Pt π contributions. Voronoi Deformation Density charges further confirms the occurrence of N←Pt π interactions. Moreover, the Energy Decomposition Analysis-Natural Orbital for Chemical Valence (EDA-NOCV) method shows that the strength of the N←Pt π interaction is not negligible by contributing to about 30-40% of the total orbital interaction. Finally, the well-known ν blue-shift occurring upon coordination to Pt, has been thoroughly investigated by exploiting the EDA-NOCV and by evaluating ν and force constants. The origin of the ν blue-shift in these systems has been discussed on the basis of the CN bond polarization. N←Pt π backbonding causes only a systematic decrease of the observed ν blue-shift when compared to the one calculated for RCN-X (X = H, alkaline, Lewis acids) herein reported (X = purely σ acceptors).