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Cited by 19Metalloenzymes and iron-sulfur proteinsOrganometallic Complex Synthesis and CatalysisMetal-Catalyzed Oxygenation Mechanisms

Necessity of fine tuning in Mo(iv) bis(dithiolene) complexes to warrant nitrate reduction

Majumdar, Amit, Pal, Kuntal, Sarkar, Sabyasachi·2009·Dalton Transactions
DOI 10.1039/b815436h
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Abstract

Four desoxo Mo(iv) bis(dithiolene) complexes, [Et(4)N][Mo(IV)(PPh(3))(SC(6)H(4)-p-Me)(mnt)(2)] () (mnt = maleonitrile dithiolate), [PNP][Mo(IV)(PPh(3))(SC(6)H(4)-o-COOH)(mnt)(2)].CH(3)CN.(i)PrOH () (PNP is [Ph(3)PNPPh(3)](+)), [Et(4)N][Mo(IV)(PPh(3))(NCS)(mnt)(2)] () and [Et(4)N](2)[Mo(IV)(NCS)(2)(mnt)(2)] () are synthesized and characterized structurally. Complexes and are found to release the pentacoordinated species, [Mo(IV)(SR)(mnt)(2)](1-) (R = -C(6)H(4)-o-COOH, -C(6)H(4)-p-Me) due to the dissociation of coordinated PPh(3) in solution and this pentacoordinated species can then reduce nitrate to nitrite. But unlike the model complex of nitrate reductase, [Et(4)N][Mo(IV)(PPh(3))(SPh)(mnt)(2)] () (A. Majumdar, K. Pal and S. Sarkar, J. Am. Chem. Soc. 2006, 128, 4196), these reactions remain incomplete. Such inefficiency of complexes and to mediate a complete reduction of nitrate is attributed to the steric bulk exerted by the para-methyl and ortho-carboxylic acid functionalities thereby retarding the formation of the nitrate bound Mo(iv) complex necessary for nitrate reduction. Complex does not release a pentacoordinated species in solution and hence is unable to reduce nitrate. Although dissociates one coordinated NCS ligand in solution to release a penta-coordinated species {[Mo(IV)(NCS)(mnt)(2)]}(1-), which remains inactive towards nitrate reduction indicating the necessity of thiolate coordination and hence the necessity of fine electronic tuning to effect nitrate reduction. Complexes , and can be converted to or depending on the amount of thiocyanate employed. Complexes and undergo a facile interconversion among themselves. Substitution of essential thiolate coordination rather than replacing the dissociable PPh(3) in and by thiocyanate resulted in inactivation (formation of ) towards nitrate reduction which is somewhat similar to the dead-end type inhibition often encountered in native systems. These results followed by theoretical calculations at DFT level establish the necessity of fine stereoelectronic tuning at the axial position of desosxo molybdenum bis(dithiolene) complexes to warrant nitrate reduction.

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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 [148]

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Authors
Majumdar, A., Pal, K., & Sarkar, S.
Affiliations
Indian Institute of Technology Kanpur (IN)
Corresponding author
Sarkar, Sabyasachi
ORCID
Venue
Dalton Transactions
Publisher
Royal Society of Chemistry (RSC)
Published
2009
Issue
11
Pages
1927
ISSN
  • 1477-9226 (ISSN-L)
  • 1477-9234
DOI
10.1039/b815436h
OpenAlex
W2152258331
Cited by
19
References
50
Citations by year
2025: 2 · 2024: 1 · 2019: 1 · 2017: 2 · 2016: 1 · 2014: 3 · 2013: 2 · 2012: 1
FWCI
1.09
Type
journal article
Language
en
Open access
closed
Locations
  • Dalton Transactions (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
nitrate reduction, nitrite reduction, thiocyanate ligands, steric effects, thiolate coordination, ligand exchange
MeSH terms
Molybdenum, Nitrates, Organometallic Compounds, Oxidation-Reduction, Thiocyanates, Crystallography, X-Ray

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