On the Geometrical Stability of Square-Planar Platinum(0) Complexes That Bear a PNP-Pincer-Type Phosphaalkene Ligand...

The four-coordinate Pt⁰ complex [Pt(PPh₃ )(Eind₂ -BPEP)] (Eind=1,1,3,3,5,5,7,7-octaethyl-1,2,3,5,6,7-hexahydro-s-indacen-4-yl; BPEP=2,6-bis(1-phenyl-2-phosphaethenyl)pyridine), which bears a PNP-pincer-type phosphaalkene ligand (Eind₂ -BPEP; PNP=N,N-bis(diphenylphosphine)-2,6-diaminopyridine), were found to adopt a square-planar configuration around the Pt center (τ₄ =0.11). This coordination geometry is very uncommon for formal d¹⁰ complexes. In this study, a series of ligands with different electronic properties (i.e., DMAP, 2,6-lutidine, PMe₃ , tBuNC, and CO) were introduced in place of PPh₃ , and their effects on the coordination geometry were examined. X-ray diffraction analysis revealed that all complexes adopted a square-planar configuration (τ₄ =0.20-0.27). In contrast, DFT calculations indicated that the geometrical stability towards distortion around Pt varied with the ligand. The complexes with pyridine-based ligands had rigid planar structures, whereas those with π-accepting ligands, such as CO, were relatively flexible towards distortion. The electronic effects of the ligands were reflected in the spectroscopic properties of the complexes, which showed a large color change in the near-infrared region.