Simple ligand-field theory of d4 and d6 transition metal complexes with a C3 symmetry axis

Inorganic Chemistry
Bruce R McGarvey, Joshua Telser

Abstract

There have been a number of recent studies reporting high-spin d(4,6) complexes with three- and four-coordinate geometry, which exhibit roughly trigonal symmetry. These include complexes of Fe(II) with general formula L(3)FeX, where L = thioether or dialkylphosphine donors of a tripodal chelating ligand and X is a monodentate ligand on the C(3) axis. In these systems, there is unquenched orbital angular momentum, which has significant consequences on the electronic/magnetic properties of the complexes, including magnetic susceptibility, EPR spectra, and magnetic Mössbauer spectra. We describe here a simple model using a description of the d orbitals with trigonal symmetry that along with the application of the spin-orbit interaction successfully explains the magnetic properties of such systems. These d orbitals with 3-fold symmetry are complex orbitals with a parameter, a, that is determined by the bond angle, α, of LFeX. We demonstrate that the E symmetry states in such systems with S > 1/2 cannot be properly "simulated by" or be "represented by" the Zeeman and second-order zero-field spin Hamiltonian alone because by definition the parameters D and E are second-order terms. One must include the first-order spin-orbit interact...Continue Reading

References

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Citations

Aug 20, 2014·Journal of the American Chemical Society·George E CutsailBrian M Hoffman
Jul 23, 2015·Journal of the American Chemical Society·Valentin V NovikovRichard E P Winpenny
Oct 10, 2015·Inorganic Chemistry·Gayan B WijeratneJoshua Telser
Aug 27, 2014·Journal of the American Chemical Society·Hsiu-Jung LinJeremy M Smith
Jan 26, 2013·Journal of the American Chemical Society·Renaud RuampsNathalie Guihéry
Apr 17, 2013·Journal of the American Chemical Society·Silvia Gomez-CocaEliseo Ruiz
Oct 1, 2016·The Journal of Physical Chemistry Letters·Alexander A PavlovValentin V Novikov
Mar 12, 2015·Physical Chemistry Chemical Physics : PCCP·Harry RamanantoaninaClaude Daul
Sep 5, 2017·Physical Chemistry Chemical Physics : PCCP·Takeshi YamaneTakeji Takui
Jul 18, 2017·European Journal of Inorganic Chemistry·Hannah E ColmerJoshua Telser
Jan 16, 2015·Chemistry : a European Journal·Marko PerićMaja Gruden-Pavlović
Aug 22, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Ruth A JuarezHaobin Wang
Apr 25, 2014·Inorganic Chemistry·Renaud RuampsNathalie Guihéry
Aug 7, 2018·Journal of the American Chemical Society·McKenna K GoetzJohn S Anderson

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