期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 139, 期 20, 页码 6843-6846出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b03287
关键词
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资金
- National Science Foundation [CHE-1566474]
- Welch Foundation [A-1423]
- Texas AM University
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1566474] Funding Source: National Science Foundation
With the view of developing self-activating electrophilic catalysts, we are now investigating complexes with a Lewis acidic moiety in the immediate vicinity of the transition metal center. Toward this end, we have synthesized a platinum complex in which the metal is connected to a Lewis acidic bis(triflato)stiboranyl ligand. This complex, ((o-(Ph2P)C6H4)(2)SbOTf2)PtCl (2), which was obtained by treatment of ((o-(Ph2P)C6H4)(2)SbCl2)PtCl (1) with 2 equiv of AgOTf, is surprisingly air stable. Yet, it promptly reacts with cyclohexylisocyanide to afford the dicationic chlorostibine complex [((o-(Ph2P)C6H4)(2)SbCl)PtCNCy](2+) ([3](2+)) as a bis-triflate salt. Formation of [3](2+) occurs through abstraction of the platinum-bound chloride ligand by the adjacent Lewis acidic antimony center. This halide migration reaction leads to activation of the platinum center. In turn, 2 behaves as a self-activating catalyst in reactions involving alkynes and readily mediates both enyne cyclization and intramolecular hydroarylation reactions, at room temperature, without addition of a chloride abstracting reagent. These results demonstrate that the coordination non-innocence of antimony ligands can be exploited for the purpose of electrophilic catalysis.
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