期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 133, 期 46, 页码 18673-18683出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja204665s
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资金
- JSPS
- Japan Science and Technology Agency (JST), Japan
- US-NSF [0848931]
- Grants-in-Aid for Scientific Research [22105010, 11J03002, 21245027] Funding Source: KAKEN
- Direct For Mathematical & Physical Scien [0848931] Funding Source: National Science Foundation
- Division Of Chemistry [0848931] Funding Source: National Science Foundation
High-valent tantalum complexes having redox-active alpha-diimine ligands, (alpha-diimine)TaCln (n = 3,4), are prepared by the reaction of TaCl5, alpha-diimine ligands, and an organosilicon-based reductant, 1-methyl-3,6-bis(trimethylsilyl)-1,4-cyclohexadiene. Reductive cleavage of the C-Cl bond of polyhaloalkanes is accomplished by trichlorotantalum complexes having dianionic alpha-diimine ligands via electron transfer from the dianionic ligands, whereas oxidative decomposition of tetraphenylborate is observed using tetrachlorotantalum complexes with monoanionic alpha-diimine ligands through electron transfer to the monoanionic ligands. Chemically oxidized or reduced complexes of (alpha-diimine)TaCl4 are isolated as ligand-centered redox products, [Cp2Co][(alpha-diimine)TaCl4] and [(alpha-diimine)TaCl4][WCl6], where the alpha-diimine ligand coordinates to the metal center as a dianionic or neutral ligand, respectively. On the basis of EPR measurements of (alpha-diimine)TaCl4 complexes (which are key intermediates for reductive cleavage of C-Cl bond and oxidative decomposition of tetraphenylborate), two redox isomers-a tantalum-centered radical and ligand-localized radical-are present in solution.
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