CoChat
Sign Up
Cited by 33Metalloenzymes and iron-sulfur proteinsOrganometallic Complex Synthesis and CatalysisMetal-Catalyzed Oxygenation Mechanisms

Selectivity of Thiolate Ligand and Preference of Substrate in Model Reactions of Dissimilatory Nitrate Reductase

Majumdar, Amit, Pal, Kuntal, Sarkar, Sabyasachi·2008·Inorganic Chemistry
DOI 10.1021/ic7024268
Open this paper in CoChat — free account

Abstract

Complexes analogous to the active site of dissimilatory nitrate reductase from Desulfovibrio desulfuricans are synthesized. The hexacoordinated complexes [PPh 4][Mo (IV)(PPh 3)(SR)(mnt) 2] (R = -CH 2CH 3 ( 1), -CH 2Ph ( 2)) released PPh 3 in solution to generate the active model cofactor, {Mo (IV)(SR)(mnt) 2} (1-), ready with a site for nitrate binding. Kinetics for nitrate reduction by the complexes 1 and 2 followed Michaelis-Menten saturation kinetics with a faster rate in the case of 1 ( V Max = 3.2 x 10 (-2) s (-1), K M = 2.3 x 10 (-4) M) than that reported earlier ( V Max = 4.2 x 10 (-3) s (-1), K M = 4.3 x 10 (-4) M) ( Majumdar, A. ; Pal, K. ; Sarkar, S. J. Am. Chem. Soc. 2006, 128, 4196- 4197 ). The oxidized molybdenum species may be reduced back by PPh 3 to the starting complex, and a catalytic cycle involving [Bu 4N][NO 3] and PPh 3 as the oxidizing and reducing substrates, respectively, is established with the complexes 1 and 2. Isostructural complexes, [Et 4N][Mo (IV)(PPh 3)(X)(mnt) 2] (X = -Br ( 3), -I ( 4)) did not show any reductive activity toward nitrate. The selectivity of the thiolate ligand for the functional activity and the cessation of such activity in isostructural halo complexes demonstrate the necessity of thiolate coordination. Electrochemical data of all these complexes correlate the ability of the thiolated species for such oxotransfer activity. Compounds 1 and 2 are capable of reducing substrates like TMANO or DMSO, but after the initial 15-20% conversion, the product trimethylamine or dimethylsulfide formed interacts with the active parent complexes 1 and 2 thereby slowing down further oxo-transfer reaction similar to feedback type reactions. From the functional nitrate reduction, the molybdenum species finally reacts with the nitrite formed leading to nitrosylation similar to the NO evolution reaction by periplasmic nitrate reductase from Pseudomonas dentrificans. All these complexes ( 1- 4) are characterized structurally by X-ray, elemental analysis, electrochemistry, electronic, FT-IR, mass and (31)P NMR spectroscopic measurements.

Integrity signals

Registry

Crossref · 10.1021/ic7024268

Cites

42 of 42 references verified0 citation errors · 0 not checkable

Statistics

Recomputing p-values needs the paper’s full text.

Claims the paper makes

This paper’s full text isn’t openly available, so its claims and self-check weren’t run. The registry and citation checks still apply.

Claims other papers make about this one

Each is checked against this paper’s own text: does it say what the citing paper says it does?

  • 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 [198]

Cites

Flagged first, then by citations

Cited by

Sorted by citations

Related

Authors
Majumdar, A., Pal, K., & Sarkar, S.
Affiliations
Indian Institute of Technology Kanpur (IN)
Corresponding author
Sarkar, Sabyasachi
ORCID
Venue
Inorganic Chemistry
Publisher
American Chemical Society (ACS)
Published
2008-03-13
Volume
47
Issue
8
Pages
3393-3401
ISSN
  • 0020-1669 (ISSN-L)
  • 1520-510X
DOI
10.1021/ic7024268
OpenAlex
W1989813523
Cited by
33
References
42
Citations by year
2026: 1 · 2025: 1 · 2023: 1 · 2021: 3 · 2019: 1 · 2017: 1 · 2016: 1 · 2015: 4 · 2014: 3 · 2013: 2 · 2012: 1
FWCI
2.65
Type
journal article
Language
en
Open access
closed
Locations
  • Inorganic Chemistry (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
reduction, dissimilatory nitrate reductase, Desulfovibrio desulfuricans, molybdenum complexes, phosphine ligands, Michaelis-Menten kinetics, catalytic cycle, trimethylamine, dimethyl sulfide
MeSH terms
Dimethyl Sulfoxide, Kinetics, Ligands, Models, Molecular, Molecular Conformation, Substrate Specificity, Sulfhydryl Compounds, Nitrate Reductase

About these checks

Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.

Statistics and arithmetic are recomputed, not judged.

Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.

What counts as a claim ›How we measure confidence ›How we check this ›

Are you an author, or do you see a problem with this page? Request a review