An Analogue System Displaying All the Important Processes of the Catalytic Cycles Involving Monooxomolybdenum(VI) and Desoxomolybdenum(IV) Centers
Abstract
The mononuclear monooxomolybdenum(VI) complex hydrotris(3,5-dimethyl-1-pyrazolyl)borato(bis-4-ethoxyphenolato)oxomoylybdenum(VI) cation, [LMoVIO(p-OC6H4-OC2H5)2]+, where L- = hydrotris(3,5-dimethyl-1-pyrazolyl)borate, has been synthesized by chemical and electrochemical oxidation from the corresponding neutral oxomolybdenum(V) species, LMoVO(p-OC6H4-OC2H5)2. The molybdenum(VI) species has been characterized by NMR, IR, and resonance Raman spectroscopies, mass spectrometry, and electronic spectroscopy. Acetonitrile solutions of cationic [LMoVIO(p-OC6H4-OC2H5)2]+ react with tertiary phosphines (PR3) to generate phosphineoxide-bound adducts, [LMoIV(OPR3)(p-OC6H4-OC2H5)2]+, which subsequently generate the cationic desoxo species, [LMoIV(p-OC6H4-OC2H5)2]+ and OPR3. In the presence of water and an oxidizing agent the desoxo species generates the monooxomolybdenum(V), LMoVO(p-OC6H4-OC2H5)2, and completes the catalytic cycle. The oxygen atom transfer reaction has been probed by isotope-labeling experiments, vibrational spectroscopies, and mass spectrometry. This study describes an analogue complex that can exhibit all important processes of the catalytic cycle involving monooxomolybdenum(VI) and desoxomolybdenum(IV) centers.
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The involvement of a proton in the reaction has been demonstrated with model compounds.
“The involvement of a proton in the reaction has also been demonstrated with model compounds.173–177”
From Nitrate and periplasmic nitrate reductases (2014) · cites this paper as [173]
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- Authors
- Nemykin, V. N., Davie, S. R., Mondal, S., Rubie, N., Kirk, M. L., Somogyi, A., & Basu, P.
- Affiliations
- University of Arizona (US)
- The Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, Pennsylvania 15282, and The Department of Chemistry, The University of Arizona, Tucson, Arizona 85721, and The Department of Chemistry, The University of New Mexico, Albuquerque, New Mexico 87131-1096.
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2002-01-12
- Volume
- 124
- Issue
- 5
- Pages
- 756-757
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W2021131903
- Cited by
- 41
- References
- 25
- Citations by year
- 2025: 1 · 2016: 2 · 2015: 2 · 2014: 3 · 2013: 1 · 2012: 2
- FWCI
- 3.33
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Journal of the American Chemical Society (publishedVersion)
- PubMed (publishedVersion)
- Funders
- National Institute of General Medical Sciences (GM 05738, GM 615501)
- Topics
- Physical Sciences › Chemistry › Inorganic Chemistry › Metal-Catalyzed Oxygenation Mechanisms
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › Metalloenzymes and iron-sulfur proteins
- Physical Sciences › Chemistry › Organic Chemistry › Organometallic Complex Synthesis and Catalysis
- Keywords
- oxygen atom transfer, tertiary phosphines, isotopic labeling, resonance Raman spectroscopy, electrochemical oxidation
- MeSH terms
- Binding Sites, Catalysis, Molybdenum, Organometallic Compounds, Oxidation-Reduction, Spectrometry, Mass, Electrospray Ionization
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