Oxo sulfido ligand substitution in dimolybdate ([Mo2O7]2-): reaction sequence and characterization of the final product, [MoS3(OSiMe3)]-

Do, Youngkyu; Simhon, E. D.; Holm, R. H.

doi:10.1021/ic00206a028

Cited by 34 publications

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“…While silylation of MoO and WO groups is not an extensively investigated reaction type, a number of stable Mo V (OSiR 3 )/Mo V O(OSiR 3 ), Mo VI O(OSiR 3 ), Mo VI O 2 (OSiR 3 ), and Mo VI S 3 (OSiR 3 ) species have been formed in this way. The only examples of silylation of a WO group of which we are aware are in the systems [(C 5 Me 5 ) 2 WO]/Me 3 SiCl40a and [(MeC 5 H 4 ) 2 WO/Me 3 SiX (X = Cl, I) 40b.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Structures, and Oxo Transfer Reactivity of Bis(dithiolene)tungsten(IV,VI) Complexes Related to the Active Sites of Tungstoenzymes

et al. 1998

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A series of bis(dithiolene)tungsten(IV,VI) complexes derived from benzene-1,2-dithiolate (bdt) has been prepared as an synthetic approach to pterin dithiolene-bound active sites of tungstoenzymes, one example of which, a archaeal oxidoreductase, has been established crystallographically (Chan et al. Science 1995, 267, 1463). With [WIVO(bdt)2]2- (2) as the starting compound, silylation with RR‘2SiCl afforded [WIV(bdt)2(OSiRR‘2)]1- (4). Oxidation of 4 with Me3NO gave [WVIO(bdt)2(OSiRR‘2)]1- (5), also accessible by silylation of [WVIO2(bdt)2]2- (3). Reaction of 3 or 5 with Me3SiCl resulted in [WVIO(bdt)2Cl]1- (6), from which the unstable species [WVIO(bdt)2L]1- (L = ButO-, PhS-) were generated in solution. Reductive oxo transfer of 6 with L‘ = P(OEt)3 or ButNC/P(OEt)3 gave [WIV(bdt)2L‘2] (8 and 9). Sulfido complex [WVIS(bdt)2(OSiRR‘2)]1- (12) was obtained in the reaction systems 4/(PhCH2S)2S and 5/(Me3Si)2S. Structures of [WO(SPh)4]1- and [W(bdt)3]2- and eight complexes of types 4−6, 8, 9, and 12 were determined by X-ray crystallography. Complexes 4 and 5 are tungsten analogues of the desoxo Mo(IV) and monooxo Mo(VI) states of Rhodobacter sphaeroides DMSO reductase. Six types of reactivity, including oxygen atom transfer, are recognized by the synthesis and interconversion of the set of complexes. The potential biological relevance of these complexes to the structure and function of active sites in two families of tungstoenzymes is considered (RR‘2 = Me3 (4); ButMe2 (4 and 5), ButPh2 (4, 5, and 12)).

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Section: Resultsmentioning

confidence: 99%

Synthesis, Structures, and Oxo Transfer Reactivity of Bis(dithiolene)tungsten(IV,VI) Complexes Related to the Active Sites of Tungstoenzymes

et al. 1998

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“…7 In order to endow the molybdate dianion with solubility in organic media, we prepared [ by-product identied by a signal at À3.8 ppm. 9 A new characteristic carbonyl stretch at 1638 cm À1 could also be observed by IR spectroscopy. 10 A preliminary X-ray crystal structure of the CO 2 -addition product revealed a k 2 -bound carbonate moiety and enabled us to formulate the major product obtained as [ , and the structure obtained in the ensuing crystallographic investigation is shown in Fig.…”

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confidence: 82%

“…24 A test reaction revealed a new resonance at d ¼ 8.73 ppm ( 1 H NMR spectroscopy), this being located in a region characteristic for formyl protons, as well as a new molybdenum species having a 95 Mo NMR signal at À23.7 ppm, a shi essentially identical to that reported for the [MoO 3 (OSiMe 3 )] À anion. 9 The production of formate improves from 16% to 71% if the reaction is run under an atmosphere of CO 2 , raising the question of whether the active species facilitating CO 2 reduction is the monocarbonate complex [MoO 3 (k 2 -CO 3 )] 2À or the dicarbonate complex [MoO 2 (k 2 -CO 3…”

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Uptake of one and two molecules of CO₂ by the molybdate dianion: a soluble, molecular oxide model system for carbon dioxide fixation

et al. 2014

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“…The latter is difficult because the substitution is often accompanied by reduction of the metal center and/or metal-oxygen framework degradation. 29 In order to overcome these difficulties, Klemperer and coworkers have chosen to substitute oxygen by sulfur in poorly reducible TavO and NbvO groups previously introduced in a Lindqvist framework. They firstly succeeded in synthesizing the isolable early-transition-metal d 0 polyoxothioanions, [TaW 5 O 18 S] 3− and [NbW 5 O 18 S] 3− .…”

Section: Introductionmentioning

confidence: 99%

Redox and acidic properties of chalcogenido-substituted mixed-metal polyoxoanions: a DFT study of α-[PW₁₁O₃₉ME]⁴⁻ (M = Nb, Ta; E = O, S, Se)

Zhang

et al. 2015

Inorg. Chem. Front.

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The redox and acidic properties of α-Keggin anions [PW 11 O 39 ME] 4− (M = Nb, Ta; E = O, S, Se) have been investigated by using the density functional theory (DFT) method. The calculated results for the studied clusters are consistent with the hypothesis that the substitution of one O atom by S or Se atoms in polyoxometalates (POMs) modifies the relative energy of the lowest unoccupied molecular orbital, inducing slight changes in the redox properties of POMs. The electronic structures and reduction energies of [PW 11 O 39 ME] 4− (M = Nb, Ta; E = O, S, Se) confirm that the substitution of one O atom by S and Se atoms in POMs enhances the redox properties, which is in good agreement with the cyclic voltammetry characterization of α-[PW 11 NbO 40 ] 4− and α-[PW 11 NbSO 39 ] 4− . The bonding energies for adding the first proton to the anions and for ammonia coordination to the protonated α-[PW 11 O 39 NbE] 4− (E = O, S, Se) were simulated to study the basicity of external oxygen sites and the acidity. The results show that the protonation energy becomes more positive after substitution by S and Se, indicating that the substitution enhances the acidity of POMs. The adsorption energy of ammonia in the case of α-[PW 11 O 39 NbE] 4− (E = S, Se) is more negative than that of α-[PW 11 O 40 NbO] 4− , which also provides the same result as mentioned above.

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Oxo sulfido ligand substitution in dimolybdate ([Mo2O7]2-): reaction sequence and characterization of the final product, [MoS3(OSiMe3)]-

Cited by 34 publications

References 3 publications

Synthesis, Structures, and Oxo Transfer Reactivity of Bis(dithiolene)tungsten(IV,VI) Complexes Related to the Active Sites of Tungstoenzymes

Synthesis, Structures, and Oxo Transfer Reactivity of Bis(dithiolene)tungsten(IV,VI) Complexes Related to the Active Sites of Tungstoenzymes

Uptake of one and two molecules of CO₂ by the molybdate dianion: a soluble, molecular oxide model system for carbon dioxide fixation

Redox and acidic properties of chalcogenido-substituted mixed-metal polyoxoanions: a DFT study of α-[PW₁₁O₃₉ME]⁴⁻ (M = Nb, Ta; E = O, S, Se)

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Oxo sulfido ligand substitution in dimolybdate ([Mo2O7]2-): reaction sequence and characterization of the final product, [MoS3(OSiMe3)]-

Cited by 34 publications

References 3 publications

Synthesis, Structures, and Oxo Transfer Reactivity of Bis(dithiolene)tungsten(IV,VI) Complexes Related to the Active Sites of Tungstoenzymes

Synthesis, Structures, and Oxo Transfer Reactivity of Bis(dithiolene)tungsten(IV,VI) Complexes Related to the Active Sites of Tungstoenzymes

Uptake of one and two molecules of CO2 by the molybdate dianion: a soluble, molecular oxide model system for carbon dioxide fixation

Redox and acidic properties of chalcogenido-substituted mixed-metal polyoxoanions: a DFT study of α-[PW11O39ME]4− (M = Nb, Ta; E = O, S, Se)

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Uptake of one and two molecules of CO₂ by the molybdate dianion: a soluble, molecular oxide model system for carbon dioxide fixation

Redox and acidic properties of chalcogenido-substituted mixed-metal polyoxoanions: a DFT study of α-[PW₁₁O₃₉ME]⁴⁻ (M = Nb, Ta; E = O, S, Se)