CHARACTERIZATION AND ELECTRONIC STRUCTURES OF TRIGONAL-BIPYRAMIDAL NICKEL(2) COMPLEXES

The preparation and characterization of several complexes of the types Ni(PR3)2(CN)2 and Ni(PR3)3-(CN)2 are reported. The four-coordinate complexes have the trans-planar structure, whereas the five-coordinate complexes have the trans-trigonal-bipyramidal structure. A self-consistent charge and configuration (SCCC) molecular orbital calculation is reported for a model trigonal-bipyramidal system of the type trans-Ni(PR3)3(CN)2. Based on this model, electronic spectral assignments are made for trans-Ni[PhP(OCH3)2]3(CN)2, and electronic factors affecting the structure of low-spin d8 systems are discussed in some detail. © 1968, American Chemical Society. All rights reserved.