Implementing the Ambiphilicity of an Organotellurenyl Cation for the Synthesis of a Platinum(II)‐Based Carboxylate‐Bridged Heterobimetallic Complex: Structure and Bonding Analysis

Abstract

AbstractThe metathesis reaction of aryltellurium chloride, ppyTeCl [ppy=2‐(2’‐pyridyl)phenyl] (5) with AgClO4 afforded Intramolecular Chalcogen Bonding (IChB)‐stabilized organotellurenyl cation [ppyTe] ⋅ ClO4 ([6] ⋅ ClO4). The reaction of [6] ⋅ ClO4 with K2PtCl4 in acetic acid resulted in the formation of platinum(II)‐based carboxylate‐bridged heterobimetallic complex [Pt(ppyTe)(μ‐OOCMe)Cl2], 7 containing an organotellurenyl cation as ligand. This is the first time a Pt(II) complex of an organotellurenyl cation donor‐acceptor ligand has been reported. Complex 7 was characterized by multi‐nuclear NMR spectroscopy (1H, 13C, and 125Te), FT‐IR spectroscopy, CHN analysis, and single‐crystal X‐ray diffraction studies. The single‐crystal X‐ray diffraction studies and DFT analysis infer that the Te center in 7 behaves as an ambiphilic ligand, accepting electrons from the N‐atom of the ppy moiety and the O‐atom of the carboxylate groups while simultaneously donating electrons to the Pt(II) center. The 2D‐fingerprint plots derived from the Hirshfeld surface analysis reveal multiple intermolecular interactions in the packing diagrams of complex 7. The natural charges accumulated on the atoms in complex 7 were calculated by Natural Population Analysis (NPA). In addition, the HOMO‐LUMO energy gap in 7 was calculated.