期刊
SCIENCE
卷 365, 期 6458, 页码 1138-+出版社
AMER ASSOC ADVANCEMENT SCIENCE
DOI: 10.1126/science.aax4423
关键词
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资金
- NIH [GM-115815]
- Dreyfus Foundation
- Harvard University
- Fannie and John Hertz Foundation
- National Science Foundation
- NSF [CHE-1454455]
- Alfred P. Sloan Foundation
- U.S. Department of Energy Office of Science and Office of Basic Energy Sciences [DE-AC02-76SF00515]
- Department of Energy's Office of Biological and Environmental Research
- U.S. Department of Energy Office of Basic Energy Sciences [100487]
- NIH/HIGMS [P41GM103393]
Terminal copper-nitrenoid complexes have inspired interest in their fundamental bonding structures as well as their putative intermediacy in catalytic nitrene-transfer reactions. Here, we report that aryl azides react with a copper(I) dinitrogen complex bearing a sterically encumbered dipyrrin ligand to produce terminal copper nitrene complexes with near-linear, short copper-nitrenoid bonds [1.745(2) to 1.759(2) angstroms]. X-ray absorption spectroscopy and quantum chemistry calculations reveal a predominantly triplet nitrene adduct bound to copper(I), as opposed to copper(II) or copper(III) assignments, indicating the absence of a copper-nitrogen multiple-bond character. Employing electron-deficient aryl azides renders the copper nitrene species competent for alkane amination and alkene aziridination, lending further credence to the intermediacy of this species in proposed nitrene-transfer mechanisms.
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