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d‐electron count, ion‐pairing and diagonal twist angles in metallo‐bis(dithiolene) complexes
Author(s) -
Kirkpatrick Charles C.,
Truong John N.,
Kowert Bruce A.
Publication year - 2017
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.24524
Subject(s) - chemistry , alkali metal , diglyme , crystallography , ion , metal , transition metal , pairing , octahedron , ionic bonding , condensed matter physics , crystal structure , physics , superconductivity , solvent , biochemistry , organic chemistry , catalysis
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 R 4 N + (R = Me, Bu). The diagonal twist angle between two NiS 2 planes is found to depend on (i) the metal's d‐electron count, spanning from 0° (planar d 7 and d 8 ), to 42° (d 9 ), to 90° (pseudo‐tetrahedral d 10 ), 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.