A trans-Hyponitrite Intermediate in the Reductive Coupling and Deoxygenation of Nitric Oxide by a Tricopper–Lewis Acid Complex
Abstract
The reduction of nitric oxide (NO) to nitrous oxide (N_2O) is a process relevant to biological chemistry as well as to the abatement of certain environmental pollutants. One of the proposed key intermediates in NO reduction is hyponitrite (N_2O_2^(2–)), the product of reductive coupling of two NO molecules. We report the reductive coupling of NO by an yttrium–tricopper complex generating a trans-hyponitrite moiety supported by two μ-O-bimetallic (Y,Cu) cores, a previously unreported coordination mode. Reaction of the hyponitrite species with Brønsted acids leads to the generation of N_2O, demonstrating the viability of the hyponitrite complex as an intermediate in NO reduction to N_2O. The additional reducing equivalents stored in each tricopper unit are employed in a subsequent step for N_2O reduction to N_2, for an overall (partial) conversion of NO to N_2. The combination of Lewis acid and multiple redox active metals facilitates this four electron conversion via an isolable hyponitrite intermediate.
Additional Information
© 2016 American Chemical Society. Received: January 29, 2016; Publication Date (Web): March 30, 2016. This work was supported by Caltech and the PRF (T.A.). T.A. is grateful for Sloan, Dreyfus, and Cottrell fellowships. We thank Dr. Michael K. Takase and Lawrence M. Henling for assistance with X-ray crystallography. We thank Professor Jonas C. Peters for use of two infrared spectrometers. D.L. gratefully acknowledges a graduate fellowship from the Resnick Sustainability Institute at Caltech. The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF Chemistry Research Instrumentation award to Caltech (CHE-0639094). The authors declare no competing financial interest.Attached Files
Supplemental Material - ja6b01083_si_001.cif
Supplemental Material - ja6b01083_si_002.cif
Supplemental Material - ja6b01083_si_003.pdf
Files
Name | Size | Download all |
---|---|---|
md5:476120a31cab12ffddd6016427136df6
|
4.0 MB | Download |
md5:18b30d839d084f10f2ccb347a3af0f77
|
5.1 MB | Preview Download |
md5:2bcd8f6129809ee7ed4bb7a41cc50d97
|
7.2 MB | Download |
Additional details
- Eprint ID
- 66239
- Resolver ID
- CaltechAUTHORS:20160418-101830823
- Caltech
- American Chemical Society Petroleum Research Fund
- Alfred P. Sloan Foundation
- Camille and Henry Dreyfus Foundation
- Cottrell Scholar of Research Corporation
- Resnick Sustainability Institute
- NSF
- CHE-0639094
- Created
-
2016-04-18Created from EPrint's datestamp field
- Updated
-
2021-11-10Created from EPrint's last_modified field
- Caltech groups
- Resnick Sustainability Institute