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. 2024 Nov 26;60(95):14117-14120.
doi: 10.1039/d4cc05161k.

Pyrazolate-supported Cr3(μ3-O) cores; homovalent CrIII3 and mixed-valent CrIII2CrIV

Jessica M López-Plá  1 , Mohammed Obies  2   3 , Georgia Zahariou  4 , Michael Pissas  4 , Yiannis Sanakis  4 , John E McGrady  2 , Raphael G Raptis  1
Affiliations

Pyrazolate-supported Cr3(μ3-O) cores; homovalent CrIII3 and mixed-valent CrIII2CrIV

Jessica M López-Plá et al. Chem Commun (Camb). .

Abstract

The thermally assisted reaction of Cr(NO3)3·9H2O, 4-Cl-pzH, and Et3N yielded electrochemically active trinuclear CrIII-oxo-pyrazolate complexes with formula (Ph4P)2[Cr3(μ3-O)(μ-4-Cl-pz)6X3], X = Cl (1) and Br (2). Magnetic susceptibility measurements and EPR spectroscopy show that 1 has an antiferromagnetically coupled Cr3O-core with an S = 1/2 ground state and isotropic exchange of J = -12.7 cm-1. (Hex = -2JS1S2). Cyclic voltammetry reveals a facile reversible oxidation to the formally CrIII2CrIV analogue of 1. The UV-Vis-NIR spectra of CrIII3 and CrIII2CrIV species have been assigned with the help of DFT calculations.

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