Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2018 Jun 13;140(23):7061-7064.
doi: 10.1021/jacs.8b03927. Epub 2018 Jun 5.

CO Oxidation by N2O Homogeneously Catalyzed by Ruthenium Hydride Pincer Complexes Indicating a New Mechanism

Rong Zeng, Moran Feller, Yael Diskin-Posner, Linda J W Shimon, Yehoshoa Ben-David, David Milstein

CO Oxidation by N2O Homogeneously Catalyzed by Ruthenium Hydride Pincer Complexes Indicating a New Mechanism

Rong Zeng et al. J Am Chem Soc. .

Abstract

Both CO and N2O are important, environmentally harmful industrial gases. The reaction of CO and N2O to produce CO2 and N2 has stimulated much research interest aimed at degradation of these two gases in a single step. Herein, we report an efficient CO oxidation by N2O catalyzed by a (PNN)Ru-H pincer complex under mild conditions, even with no added base. The reaction is proposed to proceed through a sequence of O-atom transfer (OAT) from N2O to the Ru-H bond to form a Ru-OH intermediate, followed by intramolecular OH attack on an adjacent CO ligand, forming CO2 and N2. Thus, the Ru-H bond of the catalyst plays a central role in facilitating the OAT from N2O to CO, providing an efficient and novel protocol for CO oxidation.

PubMed Disclaimer

Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Homogeneous Reactions of CO and N2O
Scheme 2
Scheme 2. Reactions of Complex 15 and Formation of 16
Figure 1
Figure 1
Crystal structure of complex 16. Atoms are presented as thermal ellipsoids at 50% probability level. Hydrogen atoms, except for Ru–H, are not shown. For selected bond lengths and angles, see SI.
Scheme 3
Scheme 3. Reaction of Complex 18 with [(18-C-6)K]OH
Scheme 4
Scheme 4. Possible Mechanism
See this image and copyright information in PMC

Similar articles

See all similar articles

Cited by

See all "Cited by" articles

References

    1. Prather M. Time Scales in Atmospheric Chemistry: Coupled Perturbations to N2O, NOy, and O3. Science 1998, 279, 1339–1341. 10.1126/science.279.5355.1339. - DOI - PubMed
    2. Ravishankara A. R.; Daniel J. S.; Portmann R. W. Nitrous Oxide (N2O): The Dominant Ozone-Depleting Substance Emitted in the 21st Century. Science 2009, 326, 123–125. 10.1126/science.1176985. - DOI - PubMed
    3. Highlight:Dameris M. Depletion of the Ozone Layer in the 21st Century. Angew. Chem., Int. Ed. 2010, 49, 489–491. 10.1002/anie.200906334. - DOI - PubMed
    4. U.S. Greenhouse Gas Inventory Report: 1990–2014, U.S. EPA; https://www.epa.gov/ghgemissions/us-greenhouse-gas-inventory-report-1990...
    5. Hansen J.; Sato M. Greenhouse gas growth rates. Proc. Natl. Acad. Sci. U. S. A. 2004, 101, 16109–16114. 10.1073/pnas.0406982101. - DOI - PMC - PubMed

    1. For selected reviews on N2O chemistry, see:

    2. Tolman W. B. Binding and Activation of N2O at Transition-Metal Centers: Recent Mechanistic Insights. Angew. Chem., Int. Ed. 2010, 49, 1018–1024. 10.1002/anie.200905364. - DOI - PMC - PubMed
    3. Konsolakis M. Decomposition over Non-Noble-Metal Oxide Catalysts: Catalytic Performance, Mechanistic Considerations, and Surface Chemistry Aspects. ACS Catal. 2015, 5, 6397–6421. 10.1021/acscatal.5b01605. - DOI
    4. Severin K. Synthetic Chemistry with Nitrous Oxide. Chem. Soc. Rev. 2015, 44, 6375–6386. 10.1039/C5CS00339C. - DOI - PubMed
    5. Parmon V. N.; Panov G. I.; Uriarte A.; Noskov A. S. Nitrous oxide in oxidation chemistry and catalysis: application and production. Catal. Today 2005, 100, 115–131. 10.1016/j.cattod.2004.12.012. - DOI
    6. Pauleta S. R.; Dell’Acqua S.; Moura I. Nitrous oxide reductase. Coord. Chem. Rev. 2013, 257, 332–349. 10.1016/j.ccr.2012.05.026. - DOI
    7. Leont’ev A. V.; Fomicheva O. A.; Proskurnina M. V.; Zefirov N. S. Modern chemistry of nitrous oxide. Russ. Chem. Rev. 2001, 70, 91–104. 10.1070/RC2001v070n02ABEH000631. - DOI
    8. Lee D.-H.; Mondal B.; Karlin K. D.. Nitrogen Monoxide and Nitrous Oxide Binding and Reduction. In Activation of Small Molecules; Tolman W. B., Ed.; Wiley-VCH Verlag GmbH & Co. KGaA: Weinheim, 2006; pp 43–79.
    1. For a review on CO oxidation by N2O via single-atom catalysis, see:Schwarz H. Ménage-à-trois: Single-atom Catalysis, Mass Spectrometry, and Computational Chemistry. Catal. Sci. Technol. 2017, 7, 4302–4314. 10.1039/C6CY02658C. - DOI

    1. For selected heterogeneous CO oxidation by N2O, see:

    2. McCabe R. W.; Wong C. Steady-State Kinetics of the CO-N2O Reaction over an Alumina-Supported Rhodium Catalyst. J. Catal. 1990, 121, 422–431. 10.1016/0021-9517(90)90250-N. - DOI
    3. Belton D. N.; Schmieg S. J. Kinetics of CO Oxidation by N2O over Rh(111). J. Catal. 1992, 138, 70–78. 10.1016/0021-9517(92)90007-5. - DOI
    4. Sadhankar R. R.; Ye J.; Lynch D. T. N2O Reducation by CO over an Alumina-Supported Pt Catalyst: Steady-State Multiplicity. J. Catal. 1994, 146, 511–522. 10.1006/jcat.1994.1089. - DOI
    5. Gluhoi A. C.; Dekkers M. A. P.; Nieuwenhuys B. E. Comparative Studies of The N2O/H2, N2O/CO, H2/O2 and CO/O2 Reactions on Supported Gold Catalysts: Effect of the Addition of Various Oxides. J. Catal. 2003, 219, 197–205. 10.1016/S0021-9517(03)00185-4. - DOI
    6. Zhdanov V. P.; Ma Y.; Matsushima T. Analysis of the Kinetics of N2O-CO reaction on Pd(110). Surf. Sci. 2005, 583, 36–45. 10.1016/j.susc.2005.03.020. - DOI
    7. Zhdanov V. P.; Nakagoe O.; Matsushima T. Kinetics of the N2O-CO reaction on Rh(110). Surf. Sci. 2007, 601, L49–L54. 10.1016/j.susc.2007.03.019. - DOI
    8. Jia A.-P.; Jiang S.-Y.; Lu J.-Q.; Luo M.-F. Study of Catalytic Activity at the CuO-CeO2 Interface for CO oxidation. J. Phys. Chem. C 2010, 114, 21605–21610. 10.1021/jp108556u. - DOI

    1. For stoichiometric CO oxidation by N2O in solution, see:

    2. Bottomley F.; Lin I. J. B.; Mukaida M. Reactions of Dinitrogen Oxide (Nitrous Oxide) with Dicyclopentadienyltitanium Complexes Including a Reaction in Which Carbon Monoxide Is Oxidized. Carbon Monoxide-Induced N–N Bond Cleavage of Nitrous Oxide That Is Competitive with Oxygen Atom Transfer to Carbon Monoxide as Mediated by a Mo(II)/Mo(IV) Catalytic Cycle. J. Am. Chem. Soc. 1980, 102, 5238–5242. 10.1021/ja00536a020. - DOI - PubMed
    3. Reeds J. P.; Yonke B. L.; Zavalij P. Y.; Sita L. R. Carbon Monoxide-Induced N–N Bond Cleavage of Nitrous Oxide That Is Competitive with Oxygen Atom Transfer to Carbon Monoxide as Mediated by a Mo(II)/Mo(IV) Catalytic Cycle. J. Am. Chem. Soc. 2011, 133, 18602–18605. 10.1021/ja208669s. - DOI - PubMed
    4. Yonke B. L.; Reeds J. P.; Zavalij P. Y.; Sita L. R. Catalytic Degenerate and Nondegenerate Oxygen Atom Transfers Employing N2O and CO2 and a MII/MIV Cycle Mediated by Group 6 MIV Terminal Oxo Complexes. Angew. Chem., Int. Ed. 2011, 50, 12342–12346. 10.1002/anie.201106074. - DOI - PubMed
    5. Xie H.; Yang L.; Ye X.; Cao Z. Mechanism of Carbon Monoxide Induced N–N Bond Cleavage of Nitrous Oxide Mediated by Molybdenum Complexes: A DFT Study. Organometallics 2014, 33, 1553–1562. 10.1021/om400935f. - DOI

    6. A related paper:

    7. Horn B.; Limberg C.; Herwig C.; Feist M.; Mebs S. CO Oxidation at Nickel Centres by N2O or O2 to Yield a Novel Hexanuclear Carbonate. Chem. Commun. 2012, 48, 8243–8245. 10.1039/c2cc33846g. - DOI - PubMed

Publication types

LinkOut - more resources