Chemistry of [Et4N][MoIV(SPh)(PPh3)(mnt)2] as an Analogue of Dissimilatory Nitrate Reductase with Its Inactivation on Substitution of Thiolate by Chloride
Abstract
Structural-functional analogue of the reduced site of dissimilatory nitrate reductase is synthesized as [Et4N][MoIV(SPh)(PPh3)(mnt)2].CH2Cl2 (1). PPh3 in 1 is readily dissociated in solution to generate the active site of the reduced site of dissimilatory nitrate reductase. This readily reacts with nitrate. The nitrate reducing system is characterized by substrate saturation kinetics. Oxotransfer to and from substrate has been coupled to produce a catalytic system, NO3- + PPh3 --> NO2- + OPPh3, where NO3- is the substrate for dissimilatory nitrate reductase. The corresponding chloro complex, [Et4N][MoIV(Cl)(PPh3)(mnt)2].CH2Cl2 (2), responds to similar PPh3 dissociation but is unable to react with nitrate, showing the indispensable role of thiolate coordination for such oxotransfer reaction. This investigation provides the initial demonstration of the ligand specificity in a model system similar to single point mutation involving site directed mutagenesis in this class of molybdoenzymes.
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Stoichiometric nitrate reduction can be achieved by inorganic molybdenum and tungsten compounds with or without dithiolene coordination.
“stoichiometric nitrate reduction can be achieved by inorganic molybdenum and tungsten compounds with148,190,198,199 or without200 dithiolene coordination.”
From Nitrate and periplasmic nitrate reductases (2014) · cites this paper as [199]
Cites
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Gold-rhodium and gold-iridium hydride clusters
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Nitrate and periplasmic nitrate reductases
Sparacino-Watkins, C., Stolz, J. F., & Basu, P. (2014) · Chem. Soc. Rev. · doi:10.1039/c3cs60249d · Cited by 426 · see citing works
Majumdar, A., Pal, K., & Sarkar, S. (2008) · Inorganic Chemistry · doi:10.1021/ic7024268 · Cited by 33 · see citing works
Self-citationNecessity of fine tuning in Mo(iv) bis(dithiolene) complexes to warrant nitrate reduction
Majumdar, A., Pal, K., & Sarkar, S. (2009) · Dalton Transactions · doi:10.1039/b815436h · Cited by 19 · see citing works
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- Authors
- Majumdar, A., Pal, K., & Sarkar, S.
- Affiliations
- Indian Institute of Technology Kanpur (IN)
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2006-03-11
- Volume
- 128
- Issue
- 13
- Pages
- 4196-4197
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W2086910210
- Cited by
- 62
- References
- 5
- Citations by year
- 2026: 7 · 2025: 5 · 2024: 1 · 2023: 3 · 2022: 1 · 2021: 3 · 2020: 4 · 2019: 2 · 2018: 2 · 2017: 1 · 2016: 1 · 2015: 2 · 2014: 3 · 2013: 3 · 2012: 2
- FWCI
- 3.87
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Journal of the American Chemical Society (publishedVersion)
- PubMed (publishedVersion)
- Topics
- Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › Metalloenzymes and iron-sulfur proteins
- Physical Sciences › Chemistry › Organic Chemistry › Organometallic Complex Synthesis and Catalysis
- Physical Sciences › Chemistry › Inorganic Chemistry › Metal-Catalyzed Oxygenation Mechanisms
- Keywords
- dissimilatory nitrate reductase, chloride substitution, nitrate reduction, substrate saturation kinetics, ligand specificity, site-directed mutagenesis, molybdenum phosphine complexes
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