Triphenylantimony(V) Catecholates Based on o-Quinones, Derivatives of Benzo[b][1,4]-Dioxines and Benzo[b][1,4]-Dioxepines

• Published in: Russian journal of coordination chemistry 2019-02, Vol.45 (2), p.133-141
• Main Authors: Poddel’skii, A. I., Okhlopkova, L. S., Meshcheryakova, I. N., Druzhkov, N. O., Smolyaninov, I. V., Fukin, G. K.
• Format: Article
• Language: English
• Subjects: Chemistry; Chemistry and Materials Science; Derivatives; Inorganic Chemistry; Oxidation; Oxygen; Physical Chemistry; Quinones; Toluene; X-ray diffraction
• ISSN: 1070-3284; 1608-3318
• DOI: 10.1134/S1070328419010093

New catecholate complexes of triphenylantimony(V), (Etgly-3,6-DBCat)SbPh 3 ( I ), (Propgly-3,6-DBCat)SbPh 3 ( II ), and (Cat-3,6-DBCat)SbPh 3 ( III ), based on analogs of sterically hindered 3,6-di- tert -butyl- o -benzoquinone, 5,8-di- tert -butyl-2,3-dihydrobenzo[ b ][1,4]dioxine-6,7-dione (L 1 ), 6,9-di- tert -butyl-2,3-dihydrobenzo[ b ][1,4]dioxepine-7,8-dione (L 2 ), and 1,4-di- tert -butyl-dibenzo[ b , e ][1,4]dioxine-2,3-dione (L 3 ), which are the 2,3-dihydrobenzo[ b ][1,4]dioxine, 2,3-dihydrobenzo[ b ][1,4]dioxepine, and dibenzo[1,4]dioxine derivatives, respectively, have been synthesized. At room temperature catecholates I and II react with molecular oxygen adding an O 2 molecule to form the corresponding spiroendoperoxides IV and  V . Catecholate III reacts with oxygen with the deep oxidation of the complex and formation of neutral o -benzoquinone. The molecular structures of complexes I and III are determined by X-ray diffraction analysis (CIF files CCDC nos. 1840299 ( I · toluene) and 1840300 ( III )).