期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 138, 期 37, 页码 12112-12123出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.6b04654
关键词
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资金
- National Institutes of Health [GM065313]
- U.S. Department of Energy, Office of Basic Energy Sciences [DE-FG02-03ER15387]
The use of hydride species for substrate reductions avoids strong reductants, and may enable nitrogenase to reduce multiple bonds without unreasonably low redox potentials. In this work, we explore the N=N bond cleaving ability of a high-spin iron(II) hydride dimer with concomitant release of H-2. Specifically, this diiron(II) complex reacts with azobenzene (PhN=NPh) to perform a four-electron reduction, where two electrons come from H-2 reductive elimination and the other two come from iron oxidation. The rate law of the H-2 releasing reaction indicates that diazene binding occurs prior to H-2, elimination, and the negative entropy of activation and inverse kinetic isotope effect indicate that H-H bond formation is the rate-limiting step. Thus, substrate binding causes reductive elimination of H-2 that formally reduces the metals, and the metals use the additional two electrons to cleave the N-N multiple bond.
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