Non-oxo 5-coordinate and 6-coordinate vanadium(iv) complexes with their precursor [LVIII(CH3OH)]0, where L = a trianionic aminetris(phenolate)-[N,O,O,O] donor ligand: a magnetostructural and EPR studyElectronic supplementary information (ESI) available: Fig. S1 contains the molecular structure of complex 1. CCDC 824885(1), 824886(2) and 824887(3) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre viawww.ccdc.cam.ac.uk/data_request/cif. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c1dt11277e

Ligating properties of a tripodal, potentially tetradentate aminetris(phenol) ligand, tris(2-hydroxy-3,5-di-tert-butylbenzyl)amine, H3L, containing [N,O,O,O] donor atoms toward the vanadium ions in +iiiand ivoxidation states have been studied. The structures of complexes 1[LVIII(CH3OH)]0, 2[LVIV(OCH3)]0and 3[LVIV(acac)]0were determined by X-ray diffraction methods as having five-coordinate V(iii), 1, five-coordinate non-oxo-vanadium(iv), 2, and six-coordinate non-oxo-vanadium(iv) 3, respectively. Compounds 1–3were also studied with electrochemical methods, variable-temperature (2–295 K) magnetic susceptibility measurements and X-band electron paramagnetic resonance (EPR) spectroscopy. The electrochemical results of 2and 3suggest metal-centered oxidation, i.e.the generation of a VV-phenolate species. EPR investigations indicate a (dxy)1ground state showing a considerable increase in the in-plane π-bonding, as is expected for a phenolate ligand. [ABSTRACT FROM AUTHOR]