CoChat
Sign Up
Cited by 86Metal-Catalyzed Oxygenation MechanismsOrganometallic Complex Synthesis and CatalysisInorganic and Organometallic Chemistry

Oxygen Atom Transfer, Coupled Electron−Proton Transfer, and Correlated Electron−Nucleophile Transfer Reactions of Oxomolybdenum(IV) and Dioxomolybdenum(VI) Complexes

Laughlin, Les J., Young, Charles G.·1996·Inorganic Chemistry
DOI 10.1021/ic950815m
Open this paper in CoChat — free account

Abstract

The oxo-Mo(IV) complexes LMoO(S(2)PR(2)-S,S') [L = hydrotris(3,5-dimethylpyrazol-1-yl)borate; R = Me, Et, Pr(i)(), Ph] were prepared by reacting MoO(S(2)PR(2))(2) and KL in refluxing toluene. The dioxo-Mo(VI) complexes cis-LMoO(2)(S(2)PR(2)-S) (R = Pr(i)(), Ph) were prepared by oxidation of the oxo-Mo(IV) complexes or by reaction of LMoO(2)Cl with NaS(2)PR(2). Oxygen atom transfers from Me(2)SO to LMoO(S(2)PR(2)) were first-order with respect to Me(2)SO and complex; the overall second-order rate constants at 40 degrees C range from 9.0(1) x 10(-)(5) M(-)(1).s(-)(1) for LMoO(S(2)PMe(2)) to 2.08(5) x 10(-)(4) M(-)(1).s(-)(1) for LMoO(S(2)PPr(2)); activation parameters were in the ranges DeltaH() = 63(1) to 73(1) kJ.mol(-)(1), DeltaS() = -88(1) to -111(1) J.K(-)(1).mol(-)(1), and DeltaG() = 100(2) kJ.mol(-)(1) for LMoO(S(2)PMe(2)) to 98(2) kJ.mol(-)(1) for LMoO(S(2)PPr(2)). Oxygen atom transfer from pyridine N-oxide to LMoO(S(2)PPr(2)) was also second-order with a rate constant of 1.54(5) x 10(-)(3) M(-)(1).s(-)(1) at 40 degrees C, DeltaH() = 62(1) kJ.mol(-)(1), DeltaS() = -90(1) J.K(-)(1).mol(-)(1), and DeltaG() = 90(1) kJ.mol(-)(1). The second-order rate laws and large negative entropies of activation are consistent with associative mechanisms for the above reactions. Oxygen atom transfer from LMoO(2)(S(2)PPr(2)) to PPh(3) was first-order with respect to reactants, with an overall second-order rate constant of 2.5(3) x 10(-)(4) M(-)(1).s(-)(1) at 30 degrees C. In toluene at 40 degrees C, all the above complexes catalyzed the oxidation of PPh(3) by Me(2)SO, with turnover rates of ca. 0.9 mol of PPh(3)/(mol of catalyst/h). Reduction of LMoO(2)(S(2)PR(2)) by SH(-) led to the generation of the dioxo-Mo(V) anions [LMoO(2)(S(2)PR(2)-S)](-), which were slowly converted to the analogous oxothio-Mo(V) complexes [LMoOS(S(2)PR(2)-S)](-). Dioxygen reacted with [LMoOS(S(2)PPr(2))](-) to produce the oxothio-Mo(VI) complex LMoOS(S(2)PPr(2)-S). The (hydroxo)oxo-Mo(V) complexes LMoO(OH)(S(2)PR(2)-S) were formed upon reduction of LMoO(2)(S(2)PR(2)) with PPh(3) in wet (3-5 M H(2)O) tetrahydrofuran or upon ferrocenium oxidation of LMoO(S(2)PR(2)) in wet tetrahydrofuran. In dry solvents, LMoO(S(2)PR(2)) were oxidized to the corresponding cations, [LMoO(S(2)PR(2)-S,S')](+), which reacted with water to form LMoO(OH)(S(2)PR(2)). The Mo(V) complexes have been characterized by EPR spectroscopy.

Integrity signals

Registry

Crossref · 10.1021/ic950815m

Cites

46 of 46 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?

  • 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 [175]

Cites

Flagged first, then by citations

Cited by

Sorted by citations

Related

Authors
Laughlin, L. J., & Young, C. G.
Affiliations
The University of Melbourne (AU)
ORCID
Young, Charles G.
Venue
Inorganic Chemistry
Publisher
American Chemical Society (ACS)
Published
1996-01-01
Volume
35
Issue
4
Pages
1050-1058
ISSN
  • 0020-1669 (ISSN-L)
  • 1520-510X
DOI
10.1021/ic950815m
OpenAlex
W2010116681
Cited by
86
References
46
Citations by year
2025: 1 · 2021: 1 · 2019: 2 · 2018: 1 · 2017: 4 · 2016: 2 · 2015: 3 · 2014: 3 · 2013: 1 · 2012: 3
FWCI
4.29
Type
journal article
Language
en
Open access
closed
Locations
  • Inorganic Chemistry (publishedVersion)
  • PubMed (publishedVersion)
Topics
  • Physical Sciences › Chemistry › Inorganic Chemistry › Metal-Catalyzed Oxygenation Mechanisms
  • Physical Sciences › Chemistry › Organic Chemistry › Organometallic Complex Synthesis and Catalysis
  • Physical Sciences › Chemistry › Organic Chemistry › Inorganic and Organometallic Chemistry
Keywords
oxygen atom transfer, proton-electron transfer, dioxomolybdenum(VI) complexes, pyridine N-oxides, pyridine, pyrazolylborate ligands, activation parameters, reaction kinetics, molybdenum oxidation state

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