Tuning Cobalt(II) Phosphine Complexes to be Axially Ambivalent

Article Chemistry, Inorganic & Nuclear

Electronic Structure and Magnetic Properties of a Low-Spin CrII Complex: trans-[CrCl2 (dmpe)2] (dmpe=1,2-Bis(dimethylphosphino)ethane)

Eva M. Zolnhofer et al.

Summary: The study characterized the ground-state electronic structure of the octahedral coordination complex trans-[CrCl2(dmpe)(2)] using high-frequency and high-field electron paramagnetic resonance (HFEPR) spectroscopy. The complex was found to have a complex electronic structure, which was well reproduced by computational methods.

INORGANIC CHEMISTRY (2021)

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Article Chemistry, Inorganic & Nuclear

A Cobalt Phosphine Complex in Five Oxidation States

Daniel A. Kurtz et al.

Summary: This report presents a study on a redox series of cobalt complexes in five sequential oxidation states, with characterization using electrochemical, spectroscopic, and crystallographic methods. The use of a simple bidentate phosphine ligand allows for isolation of the five oxidation states, with changes in coordination number and geometry as a function of the oxidation state. Single-crystal X-ray diffraction is used to characterize complexes in each oxidation state.

INORGANIC CHEMISTRY (2021)

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Article Chemistry, Multidisciplinary

Redox-Induced Structural Reorganization Dictates Kinetics of Cobalt(III) Hydride Formation via Proton-Coupled Electron Transfer

Daniel A. Kurtz et al.

Summary: The study investigates the mechanism of hydride formation through two-electron, one-proton reactions of a family of complexes. It reveals that proton transfer rate constants are correlated with the strength of the proton source and the steric bulk of the chelating diphosphine ligands, plateauing as the reaction becomes increasingly exergonic. Mechanistic studies identify the stepwise process of hydride formation involving reduction of Co(III) species, ligand dissociation, protonation, and tautomerization.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Article Chemistry, Inorganic & Nuclear