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Theoretical insights into the nature of PtSn bond: Reevaluating the bonding/back‐bonding properties of trichlorostannate with comparison to the cyano ligand

The coordinating properties of the trichlorostannate ligand in hydrido platinum trichlorostannato and platinum bis‐trichlorostannato complexes, containing various phosphine ligands, have been elucidated by means of charge decomposition analysis, the Ziegler‐Rauk Energy Decomposition with the Natural Orbitals for Chemical Valence, Domain‐Averaged Fermi Hole, and natural bond orbital methods. Trichlorostannate has been found to be a strong σ‐donor and a weak π‐acceptor ligand with coordination properties not far from those of the cyano ligand. For back‐bonding, the tin‐chlorine σ∗ orbitals are mostly responsible. In contrast to previous assumptions, the 5d orbitals of tin play no role at all in the interaction with the platinum center. QTAIM calculations suggest, that the platinum‐tin interaction should be interpreted as donor–acceptor, rather than covalent type. Trichlorostannate has been found to have weaker trans influence in comparison to the cyano ligand. © 2017 Wiley Periodicals, Inc.