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J Am Chem Soc. 2013 Oct 16;135(41):15479-88. doi: 10.1021/ja406027x. Epub 2013 Oct 3.

Gold-mediated expulsion of dinitrogen from organic azides.

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  • 1Department of Chemistry and Biochemistry, The University of Texas at Arlington , Arlington, Texas 76019, United States.


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(Cy)NN][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)NN][SbF6] from 30 to 50 °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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