A T-shaped three-coordinate nickel(I) carbonyl complex and the geometric preferences of three-coordinate d9 complexes.
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.
Eckert
Nathan A
NA
Department of Chemistry, University of Rochester, New York 14267, USA.
Dinescu
Adriana
A
Cundari
Thomas R
TR
Holland
Patrick L
PL