title: Rhenium Complex with Noninnocent Dioxolene Ligand: Combined Experimental and ab Initio Study of [(3,5-di-tert-Bu2C6H2O2)ReCl3(OPPh3)].
abstract: Reaction of [ReOCl3(PPh3)2] with 3,5-di-tert-butyl-1,2-benzoquinone (3,5-DTBQ) in hot toluene produces a new complex [(3,5-di-tert-Bu2C6H2O2)Re(OPPh3)Cl3] (1), which was isolated and characterized by elemental analysis, IR, UV-vis spectroscopy, and cyclic voltammetry. In order to clarify the charge state of rhenium and the coordinated dioxolene ligand, X-ray experiments at 150 and 290 K were carried out. The C-O, C-C, and Re-O bond distances at both 150 and 290 K fall between those for semiquinolate (3,5-DTBSQ) and catecholate (3,5-DTBCat) forms; an empirical "metrical oxidation state" of the dioxolene ligand was estimated to be -1.5. High-level ab initio calculations (SOC-CASSCF/NEVPT2) revealed a mixed valence nature of the triplet ground state of complex 1 corresponding to a superposition of the Re(IV)-SQ and Re(V)-cat forms. In agreement with the high-level ab initio and DFT calculations, the temperature dependence of the magnetic susceptibility (5-300 K) is well described in the assumption of the triplet ground state, with the anomalously large zero-field splitting (ZFS) arising from the spin-orbit coupling. According to the ab initio calculations, all absorption bands in the visible region of the electronic absorptions spectrum are assigned to the LMCT bands, with significant contribution of the intraligand transition in the most intense band at 555 nm.
authors.affiliation: †Nikolayev Institute of Inorganic Chemistry, Prospekt Lavrentyeva 3, 630090 Novosibirsk, Russia.|‡Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk, Russia.
authors.forename: Pavel A
authors.initials: PA
authors.lastname: Abramov
authors.affiliation: ‡Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk, Russia.|§Voevodsky Institute of Chemical Kinetics and Combustion, Institutskaya str. 3, 630090 Novosibirsk, Russia.
authors.forename: Nina P
authors.initials: NP
authors.lastname: Gritsan
authors.affiliation: ‡Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk, Russia.|§Voevodsky Institute of Chemical Kinetics and Combustion, Institutskaya str. 3, 630090 Novosibirsk, Russia.
authors.forename: Elizaveta A
authors.initials: EA
authors.lastname: Suturina
authors.affiliation: ‡Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk, Russia.|∥International Tomography Center, Institutskaya str. 3a, 630090 Novosibirsk, Russia.
authors.forename: Artem S
authors.initials: AS
authors.lastname: Bogomyakov
authors.affiliation: †Nikolayev Institute of Inorganic Chemistry, Prospekt Lavrentyeva 3, 630090 Novosibirsk, Russia.|‡Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk, Russia.
authors.forename: Maxim N
authors.initials: MN
authors.lastname: Sokolov
mesh_terms: D016227:Benzoquinones / Q000737:chemistry*; D056831:Coordination Complexes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008958:Models, Molecular; D011789:Quantum Theory; D012211:Rhenium / Q000737:chemistry*
chemical_list: D016227:Benzoquinones; D056831:Coordination Complexes; C054466:3,5-di-tert-butyl-1,2-benzoquinone; D012211:Rhenium