posted on 2005-10-31, 00:00authored byNathan A. Eckert, Adriana Dinescu, Thomas R. Cundari, Patrick L. Holland
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 C2v structure) contrasts with that of isosteric d9
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 d9 complexes is affected by differential charge donation
of the ligands to the metal center.