Digallane with Redox-Active Diimine Ligand: Dualism of Electron-Transfer Reactions
2014 | journal article. A publication with affiliation to the University of Göttingen.
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Digallane with Redox-Active Diimine Ligand: Dualism of Electron-Transfer Reactions
Fedushkin, I. L.; Skatova, A. A.; Dodonov, V. A.; Chudakova, V. A.; Bazyakina, N. L.; Piskunov, A. V. & Demeshko, S. et al. (2014)
Inorganic Chemistry, 53(10) pp. 5159-5170. DOI: https://doi.org/10.1021/ic500259k
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Details
- Authors
- Fedushkin, Igor L.; Skatova, Alexandra A.; Dodonov, Vladimir A.; Chudakova, Valentina A.; Bazyakina, Natalia L.; Piskunov, Alexander V.; Demeshko, Serhiy; Fukin, Georg K.
- Abstract
- The reactivity of digallane (dpp-Bian)Ga-Ga(dpp-Bian) (1), which consists of redox-active ligand 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-Bian), has been studied. The reaction of 1 with I-2 proceeds via one-electron oxidation of each of two dpp-Bian ligands to a radical-anionic state and affords complex (dpp-Bian)IGa-GaI(dpp-Bian) (2). Dissolution of complex 2 in pyridine (Py) gives monomeric compound (dpp-Bian)GaI(Py) (3) as a result of a solvent-induced intramolecular electron transfer from the metal-metal bond to the dpp-Bian ligands. Treatment of compound 3 with B(C6F5)(3) leads to removal of pyridine and restores compound 2. The reaction of compound 1 with 3,6-di-tert-butyl-orthobenzoquinone (3,6-Q) proceeds with oxidation of all the redox-active centers in 1 (the Ga-Ga bond and two dpp-Bian dianions) and results in mononuclear catecholate (dpp-Bian)Ga(Cat) (4) (Cat = [3,6-Q](2-)). Treatment of 4 with AgBF4 gives a mixture of [(dpp-Bian)(2)Ag][BF4] (5) and (dpp-Bian)GaF(Cat) (6), which both consist of neutral dpp-Bian ligands. The reduction of benzylideneacetone (BA) with 1 generates the BA radical-anions, which dimerize, affording (dpp-Bian)Ga-(BA-BA)-Ga(dpp-Bian) (7). In this case the Ga-Ga bond remains unchanged. Within 10 mm at 95 degrees C in solution compound 7 undergoes transformation to paramagnetic complex (dpp-Bian)Ga(BA-BA) (8) and metal-free compound C36H40N2 (9). The latter is a product of intramolecular addition of the C-H bond of one of the iPr groups to the C=N bond in dpp-Bian. Diamagnetic compounds 3, 5, 6, and 9 have been characterized by NMR spectroscopy, and paramagnetic complexes 2, 4, 7, and 8 by ESR spectroscopy. Molecular structures of 2-7 and 9 have been established by single-crystal X-ray analysis.
- Issue Date
- 2014
- Status
- published
- Publisher
- Amer Chemical Soc
- Journal
- Inorganic Chemistry
- ISSN
- 1520-510X; 0020-1669
- Sponsor
- Russian Science Foundation [14-13-01063]