Ivan V Smolyaninov1, Georgy K Fukin2, Nadezhda T Berberova1, Andrey I Poddel'sky2. 1. Department of Chemistry, Astrakhan State Technical University, 16 Tatisheva Str., 414056 Astrakhan, Russia. 2. G.A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 49 Tropinina Str., 603137 Nizhny Novgorod, Russia.
Abstract
A new series of triphenylantimony(V) 3-alkylthio/arylthio-substituted 4,6-di-tert-butylcatecholates of the type (3-RS-4,6-DBCat)SbPh3, where R = n-butyl (1), n-hexyl (2), n-octyl (3), cyclopentyl (4), cyclohexyl (5), benzyl (6), phenyl (7), and naphthyl-2 (8), were synthesized from the corresponding catechol thioethers and Ph3SbBr2 in the presence of a base. The crystal structures of 1, 2, 3, and 5 were determined by single-crystal X-ray analysis. The coordination polyhedron of 1-3 is better described as a tetragonal pyramid with a different degree of distortion, while that for 5- was a distorted trigonal bipyramid (τ = 0.014, 0.177, 0.26, 0.56, respectively). Complexes demonstrated different crystal packing of molecules. The electrochemical oxidation of the complexes involved the catecholate group as well as the thioether linker. The introduction of a thioether fragment into the aromatic ring of catechol ligand led to a shift in the potential of the "catechol/o-semiquinone" redox transition to the anodic region, which indicated the electron-withdrawing nature of the RS group. The radical scavenging activity of the complexes was determined in the reaction with DPPH radical.
A new series of triphenylantimony(V) n class="Chemical">3-alkylthio/arylthio-substituted 4,6-di-tert-butylcatecholates of the type (3-RS-4,6-DBCat)SbPh3, where R = n-butyl (1), n-hexyl (2), n-octyl (3), cyclopentyl (4), cyclohexyl (5), benzyl (6), phenyl (7), and naphthyl-2 (8), were synthesized from the corresponding catecholthioethers and Ph3SbBr2 in the presence of a base. The crystal structures of 1, 2, 3, and 5 were determined by single-crystal X-ray analysis. The coordination polyhedron of 1-3 is better described as a tetragonal pyramid with a different degree of distortion, while that for 5- was a distorted trigonal bipyramid (τ = 0.014, 0.177, 0.26, 0.56, respectively). Complexes demonstrated different crystal packing of molecules. The electrochemical oxidation of the complexes involved the catecholate group as well as the thioether linker. The introduction of a thioether fragment into the aromatic ring of catechol ligand led to a shift in the potential of the "catechol/o-semiquinone" redox transition to the anodic region, which indicated the electron-withdrawing nature of the RS group. The radical scavenging activity of the complexes was determined in the reaction with DPPH radical.
Authors: Ivan V Smolyaninov; Daria A Burmistrova; Maxim V Arsenyev; Maria A Polovinkina; Nadezhda P Pomortseva; Georgy K Fukin; Andrey I Poddel'sky; Nadezhda T Berberova Journal: Molecules Date: 2022-05-16 Impact factor: 4.927
Authors: Andrey I Poddel'sky; Ivan V Smolyaninov; Aleksandra I Shataeva; Evgenii V Baranov; Georgy K Fukin Journal: Molecules Date: 2022-10-01 Impact factor: 4.927