期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 135, 期 41, 页码 15479-15488出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja406027x
关键词
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资金
- National Science Foundation [CHE-0845321, CHE-1265807]
- Robert A. Welch Foundation [Y-1289]
- U.S. Department of Energy [DE-FG02-03ER15387]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1265807] Funding Source: National Science Foundation
- U.S. Department of Energy (DOE) [DE-FG02-03ER15387] Funding Source: U.S. Department of Energy (DOE)
Organoazides and their nitrogen expulsion chemistry have attracted the attention of many scientists because they serve as a useful source of nitrene fragments and interesting nitrene rearrangement products. Gold-mediated reactions are also of significant current interest. This manuscript describes several important discoveries based at the intersection of these fields. In particular, we report the first isolable gold organoazides ([(SIPr)AuN(1-Ad)NN][SbF6], [(SIPr)AuN(2-Ad)NN][SbF6] and [(SIPr)AuN(1-Ad)NN]-[SbF6]; [SbF6]; SIPr = a N-heterocyclic carbene; 1-AdNNN = 1-azidoadamantane; 2-AdNNN = 2-azidoadamantane; CyNNN = azidocyclohexane), and their gold-mediated nitrogen expulsion chemistry, and the isolation of formal nitrene rearrangement products of 1-AdN, 2-AdN and CyN (including the elusive 4-azahomoadamant-3-ene) as their gold complexes. We have also performed a computational study to understand and explain the observed structure of gold-coordinated 1-AdNNN and 2-AdNNN and their nitrogen elimination pathways, which implies that the conversion of the organoazide complex to the imine is a concerted process without a nitrene/nitrenoid intermediate. Kinetic studies of [(SIPr)AuN(2-Ad)NNN][SbF6] from 30 to 50 degrees C indicate that nitrogen elimination is a first-order process. The experimentally determined activation parameters are in good agreement with the calculated values.
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