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Updated: May 20, 2026

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Synthesis and characterization of a neutral titanium tris(iminosemiquinone) complex featuring redox-active ligands
Kensha Marie Clark1, Jesper Bendix, Alan F Heyduk
1Department of Chemistry, University of California, Irvine, California 92697, USA. kmclark@uci.edu
Abstract:
The neutral tris(semiquinonate) complex [Ti(dmp-BIAN(isq))(3)] [dmp-BIAN(isq) = N,N'-bis(3,5-dimethylphenylimino)acenaphthenesemiquinonate] was structurally, spectroscopically, and electrochemically characterized. Solid-state magnetism experiments reveal field-quenchable, enhanced temperature-independent paramagnetism (TIP). Density functional theory calculations employing the experimental geometry predicts a strong antiferromagnetic coupling, leading to an S = 0 ground state, but they also hint at spin frustration and concomitant close-lying, excited states, which cause the observed large TIP by admixture into the ground state. The dmp-BIAN(isq) ligand, which facilitates intramolecular electron transfer, was shown to undergo four quasi-reversible redox processes, demonstrating the ability of the ligand to act as an electron reservoir in complexes of early metals.
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