Valence tautomerism in a cobalt–dioxolene complex containing an imidazolic ancillary ligand†‡ † This article is dedicated to Professor Andrea Dei, brilliant teacher and far-sighted chemist.‡ Electronic supplementary information (ESI) available: Experimental details, additional crystallographic information, powder X-ray diffraction patterns, thermogravimetric analysis. CCDC 2262804 and 2262731 entries contain the supplementary crystallographic data for 1 and 2, respectively. For ESI and crystallographic data in CIF or other electronic format see DOI: https://doi.org/10.1039/d3ra03235c

ABSTRACT: This work reports the synthesis, structural, spectroscopic and magnetic investigation of two complexes, [Co(bmimapy)(3,5-DTBCat)]PF6·H2O (1) and [Co(bmimapy)(TCCat)]PF6·H2O (2), where bmimapy is an imidazolic tetradentate ancillary ligand and 3,5-DTBCat and TCCat are the 3,5-di-tert-butyl-catecholate and tetrachlorocatecholate anions, respectively. Their structures have been elucidated using single crystal X-ray diffraction, showing a pseudo-octahedral cobalt ion bound to a chelating dioxolene ligand and the ancillary bmimapy ligand in a folded conformation. Magnetometry displayed an entropy-driven, incomplete, Valence Tautomeric (VT) process for 1 in the 300–380 K temperature range, while 2 displayed a temperature independent, diamagnetic low-spin cobalt(iii)–catecholate charge distributi

SUBMITTER: Moledo Vicente Guedes A 

PROVIDER: S-EPMC10318486 | biostudies-literature | 2023 Jul

REPOSITORIES: biostudies-literature