title: d-electron count, ion-pairing and diagonal twist angles in metallo-bis(dithiolene) complexes.
abstract: Electronic structure calculations for late transition metals coordinated by two dithiolene ligands are found to be consistent with existing structures and also predict the geometries of Ni(I) species for which no solid state structures have been reported. Of particular interest are the compounds [M(mnt)2]n-(M = Ni, Pd, and Pt with n = 1, 2, 3; M = Cu with n = 2). Calculations have been performed with and without ion-paring with M(diglyme)+(M = Li, Na, K) and R4N+(R = Me, Bu). The diagonal twist angle between two NiS2planes is found to depend on (i) the metal's d-electron count, spanning from 0° (planar d7and d8), to 42° (d9), to 90° (pseudo-tetrahedral d10), and (ii) the identity of the ion-paired cations. Calculated ion-pairing energies are functions of the cation size and charge-density, being larger for alkali-metal coordinated diglyme and smaller for tetra-alkyl ammonium cations. © 2016 Wiley Periodicals, Inc.
authors: Department of Chemistry, Saint Louis University, St. Louis, Missouri, 63103.
authors: Charles C
authors: CC
authors: Kirkpatrick
authors: Department of Chemistry, Saint Louis University, St. Louis, Missouri, 63103.
authors: John N
authors: JN
authors: Truong
authors: Department of Chemistry, Saint Louis University, St. Louis, Missouri, 63103.
authors: Bruce A
authors: BA
authors: Kowert
mesh_terms: D004583:Electrons; D009942:Organometallic Compounds / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D028561:Transition Elements / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D013438:Sulfhydryl Compounds; D028561:Transition Elements
keywords: 4-coordinate bis(chelate) compounds; bis(dithiolene) compounds; copper(II); d9; diagonal twist; dithiolene compounds; electronic structure calculations; ion-pairing; metallo-bis(dithiolene) compounds; molecular orbital calculations; nickel(I)