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A three-coordinate diketiminate-nickel(I) complex with a carbonyl ligand has been characterized using EPR and IR spectroscopies and X-ray crystallography. The T geometry (bending from the sterically favored C(2)(v)() structure) contrasts with that of isosteric d(9) copper(II) complexes. DFT calculations on a truncated model reproduce experimental geometries, implying that the geometric differences are electronic in nature. Analysis of the charge distribution in the complexes shows that the geometry of the three-coordinate d(9) complexes is affected by differential charge donation of the ligands to the metal center.

A T-Shaped Three-Coordinate Nickel(I) Carbonyl Complex and the Geometric Preferences of Three-Coordinate d9 Complexes

A T-Shaped Three-Coordinate Nickel(I) Carbonyl Complex and the Geometric Preferences of Three-Coordinate d⁹ Complexes