Reduction of Bis(dithiolene)oxo(disulfido)tungsten(VI) Complex with Dihydrogen Related to the Chemical Function of the Fourth Tungsten-Containing Enzyme (WOR4) from <i>Pyrococcus furiosus</i>

Sugimoto, Hideki; Tano, Hiroyuki; Toyota, Kazuo; Tajima, Reiko; Takahashi, Isao; Hirota, Shun; Itoh, Shinobu

doi:10.1021/ja907164s

Cited by 22 publications

(19 citation statements)

References 25 publications

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“…Hydrogen atoms are shown as fixed-size spheres (radius 0.20 Å). Selected bond lengths and angles: Pt-S1, 2.2825(15); Pt-S2, 2.2825(15); C1-C2, 1.386(7); C1-S1, 1.687(5); C2-S2, 1.693(5); C1-N1, 1.687(5); C2-N2, 1.693(5); C3-N1, 1.369(7); C3-N2, 1.393(6); C3-S3, 1.660(5) Å; S1-Pt-S2, 91.89(5); S1-Pt-S2a, 88.11(5); C1-C2-S2, 123.9(4); C2-C1-S1, 124.5(4); C1-S1-Pt, 99.88(16); C2-S2-Pt, 99.8(2); N1-C1-C2, 106.6(4); N2-C2-C1, 107.7(4); C1-N1-C3, 110.8(4); C2-N2-C3, 109.4(4); N1-C3-N2, 105.6(4); N1-C3-S3, 127.1(4); N2-C3-S3, 127.4(1)1. a = 2 À x, Ày, 1 À z. See Tables S3-S11 in the ESI † for further details.…”

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confidence: 99%

Structural tailoring of the NIR-absorption of bis(1,2-dichalcogenolene) Ni/Pt electrochromophores deriving from 1,3-dimethyl-2-chalcogenoxo-imidazoline-4,5-dichalcogenolates

et al. 2016

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The choice of the metal ion M and the terminal Y and donor X chalcogen species (M = Ni, Pt; and X, Y = S, Se) in square-planar complexes deriving from 1,3-dimethyl-2-chalcogenoxo-imidazoline-4,5-dichalcogenolates allows fine-tuning of both the redox stability and the energy of the particularly intense NIR electrochromic absorption, thanks to the subtle contribution of M, X, and Y to the relevant frontier molecular orbitals, investigated at the IEF-PCM DFT and TD-DFT level

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confidence: 99%

Structural tailoring of the NIR-absorption of bis(1,2-dichalcogenolene) Ni/Pt electrochromophores deriving from 1,3-dimethyl-2-chalcogenoxo-imidazoline-4,5-dichalcogenolates

et al. 2016

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“…The targeted W VI O(S) complex could not be purified owing to the low solubility of the by-products, preventing us investigating the spectroscopic properties and reactivities. When W IV OL COOMe was treated with elemental sulfur, the disulfido-tungsten(VI) complex, [W VI O(S 2 )-(L COOMe ) 2 ] 2− was formed as found in the reactions of [W IV O-(L bdts ) 2 ] 2− (bdts = benzene-1,2-dithiolates),43,44 but the targeted compound W VI O(S)L COOMe was not obtained. The UV-vis spectral change of W IV OL COOMe was close to that of the W IV O complexes with bdts.…”

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confidence: 99%

A new series of bis(ene-1,2-dithiolato)tungsten(iv), -(v), -(vi) complexes as reaction centre models of tungsten enzymes: Preparation, crystal structures and spectroscopic properties

et al. 2013

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The carbomethoxy substituted dithiolene ligand (L(COOMe)) enabled us to develop a series of new bis(ene-1,2-dithiolato)tungsten complexes including W(IV)O, W(IV)(OSiBuPh(2)), W(VI)O(2), W(VI)O(OSiBuPh(2)) and W(VI)O(S) core structures. By using these tungsten complexes, a systematic study of the terminal monodentate ligand effects has been performed on the structural, spectroscopic properties and reactivity. The structure and spectroscopic properties of the tungsten complexes have also been compared to those of the molybdenum complexes coordinated by the same ligand to investigate the effects of the metal ion (W vs. Mo). X-ray crystallographic analyses of the tungsten(IV) complexes have revealed that the tungsten centres adopt a distorted square pyramidal geometry with a dithiolene ligand having an ene-1,2-dithiolate form. On the other hand, the dioxotungsten(VI) complex exhibits an octahedral structure consisting of the bidentate L(COOMe) and two oxo groups, in which π-delocalization was observed between the W(VI)O(2) and ene-1,2-dithiolate units. The tungsten(IV) and dioxotungsten(VI) complexes are isostructural with the molybdenum counter parts. DFT calculation study of the W(VI)O(S) complex has indicated that the W=S bond of 2.2 Å is close to the bond length between the tungsten centre and ambiguously assigned terminal monodentate atom in aldehyde oxidoreductase of the tungsten enzyme. Resonance Raman (rR) spectrum of the W(VI)O(S) complex has shown the two inequivalent L(COOMe) ligands with respect to their bonding interactions with the tungsten centre, reproducing the appearance of two ν(C=C) stretches in the rR spectrum of aldehyde oxidoreductase. Sulfur atom transfer reaction from the W(VI)O(S) complex to triphenylphosphines has also been studied kinetically to demonstrate that the tungsten complex has a lower reactivity by about one-order of magnitude, when compared with its molybdenum counterpart.

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“…Very few respective and at least fractionally functional analogues are reported in the literature. The groups of Sarkar and later Sugimoto introduced molybdenum and tungsten complexes which were found to be reactive toward polysulfide and sulfur, respectively [72][73][74]. However, the coordination of sulfido ligands is accompanied by increasing instability and reactivity as reflected in the faster sulfur atom transfer (SAT) compared to OAT (vide supra).…”

Section: Dithiolene Complexesmentioning

confidence: 99%

Inspired by Nature—Functional Analogues of Molybdenum and Tungsten-Dependent Oxidoreductases

et al. 2022

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Throughout the previous ten years many scientists took inspiration from natural molybdenum and tungsten-dependent oxidoreductases to build functional active site analogues. These studies not only led to an ever more detailed mechanistic understanding of the biological template, but also paved the way to atypical selectivity and activity, such as catalytic hydrogen evolution. This review is aimed at representing the last decade’s progress in the research of and with molybdenum and tungsten functional model compounds. The portrayed systems, organized according to their ability to facilitate typical and artificial enzyme reactions, comprise complexes with non-innocent dithiolene ligands, resembling molybdopterin, as well as entirely non-natural nitrogen, oxygen, and/or sulfur bearing chelating donor ligands. All model compounds receive individual attention, highlighting the specific novelty that each provides for our understanding of the enzymatic mechanisms, such as oxygen atom transfer and proton-coupled electron transfer, or that each presents for exploiting new and useful catalytic capability. Overall, a shift in the application of these model compounds towards uncommon reactions is noted, the latter are comprehensively discussed.

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Reduction of Bis(dithiolene)oxo(disulfido)tungsten(VI) Complex with Dihydrogen Related to the Chemical Function of the Fourth Tungsten-Containing Enzyme (WOR4) from Pyrococcus furiosus

Cited by 22 publications

References 25 publications

Structural tailoring of the NIR-absorption of bis(1,2-dichalcogenolene) Ni/Pt electrochromophores deriving from 1,3-dimethyl-2-chalcogenoxo-imidazoline-4,5-dichalcogenolates

Structural tailoring of the NIR-absorption of bis(1,2-dichalcogenolene) Ni/Pt electrochromophores deriving from 1,3-dimethyl-2-chalcogenoxo-imidazoline-4,5-dichalcogenolates

A new series of bis(ene-1,2-dithiolato)tungsten(iv), -(v), -(vi) complexes as reaction centre models of tungsten enzymes: Preparation, crystal structures and spectroscopic properties

Inspired by Nature—Functional Analogues of Molybdenum and Tungsten-Dependent Oxidoreductases

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