Oxygen, sulphur, and selenium abstraction from WCl4Y (Y = O, S, or Se) by triphenylphosphine. Crystal and molecular structure of tetrachlorobis(triphenylphosphine)tungsten(IV)

Drew, Michael G. B.; Page, E. M.; Rice, David A.

doi:10.1039/dt9830000061

Cited by 15 publications

(4 citation statements)

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“… Triethyl phosphite is an effective oxo acceptor in these reactions at ambient temperature while Ph 3 P shows slow reactivity at 60 °C. The associated reaction system [WOCl 4 ]/Ph 3 P affords trans- [WCl 4 (PPh 3 ) 2 ] . Complexes 8 and 9 are related to the bis(dithiolene) dicarbonyl [W(S 2 C 2 Me 2 ) 2 (CO) 2 ], prepared by the photochemical reaction of W(CO) 6 and [Ni(S 2 C 2 Me 2 ) 2 ] …”

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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“…39 The reaction of WECl 4 (E = O, S, Se) with a large excess of PPh 3 over several days in toluene was reported to form [WCl 4 (PPh 3 ) 2 ] and EPPh 3 . 40 Similar, but much faster abstraction of the selenium occurs on contact with alkyl phosphines. Similarly, reaction of o -C 6 H 4 (PMe 2 ) 2 with WSeCl 4 in CH 2 Cl 2 instantly produced a green solution and a brown precipitate, and the 31 P{ 1 H} NMR spectrum showed several species present in the solution, with the major resonances at δ = +20 and +33, which may be due to phosphine selenides.…”

Section: Density Functional Theory (Dft) Calculationsmentioning

confidence: 97%

“…Although WSeCl 4 was first described in 1974, 21 the few coordination complexes known are described in papers focussed rather on WSCl 4 adducts, 5,22–24 and a more detailed investigation of the selenide chloride is required to develop its chemistry and to determine if it could be the basis of a single source low pressure CVD route to WSe 2 . A small number of dual source CVD routes to WSe 2 films have been described, 19,20 including using WCl 6 and SeEt 2 in atmospheric pressure CVD, 25 however, to the best of our knowledge there are no single source CVD reagents for tungsten diselenide films.…”

Section: Introductionmentioning

confidence: 99%

Tungsten(vi) selenide tetrachloride, WSeCl₄ – synthesis, properties, coordination complexes and application of [WSeCl₄(SeⁿBu₂)] for CVD growth of WSe₂ thin films

et al. 2022

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“…The infrared spectrum was consistent with bound triphenylphosphine. Previous work identified WCl 4 (PPh 3 ) 2 as the trans isomer, based on single-crystal X-ray diffraction [37]. Compound 4 exhibited broadened and paramagnetically shifted peaks in the 1 H-NMR spectrum.…”

Section: Compound Characterizationmentioning

confidence: 98%

Improved synthetic routes to tungsten(IV) bromide complexes

Bhuiyan

Hargrove

Metz

et al. 2015

Transition Met Chem

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Convenient synthetic routes to the compounds WBr 4 (1), WBr 4 (MeCN) 2 (2), WBr 4 (THF) 2 (3), WBr 4 (PPh 3 ) 2 (4), WBr 4 (bpy) (6), and WBr 4 (dppe) (7) are described via the solution-phase oxidation of W(CO) 6 using two equivalents of bromine. These one-pot syntheses use inexpensive and readily available starting materials and produce analytically pure compounds with high yields under mild conditions. Attempts to grow crystals of 1 by heating in a sealed tube at *200°C resulted in formation of the previously reported compound WOBr 4 . Attempts to recrystallize 4 from dichloromethane solution produced [HPPh 3 ] 2 [WBr 6 ] (5). X-ray crystallographic studies showed that 5 consists of an array of [WBr 6 ] 2-anions and [HPPh 3 ] ? cations and that 7ÁCH 2 Cl 2 has the expected sixcoordinate tungsten center. The synthesis of tungsten(IV) bromide compounds via oxidation of W(CO) 6 is simple and provides better yields than previously reported methods. This synthetic route also has many advantages over the syntheses of similar tungsten(IV) chloride compounds which involve reduction of WCl 6 .

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Oxygen, sulphur, and selenium abstraction from WCl4Y (Y = O, S, or Se) by triphenylphosphine. Crystal and molecular structure of tetrachlorobis(triphenylphosphine)tungsten(IV)

Cited by 15 publications

References 4 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

Tungsten(vi) selenide tetrachloride, WSeCl₄ – synthesis, properties, coordination complexes and application of [WSeCl₄(SeⁿBu₂)] for CVD growth of WSe₂ thin films

Improved synthetic routes to tungsten(IV) bromide complexes

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Oxygen, sulphur, and selenium abstraction from WCl4Y (Y = O, S, or Se) by triphenylphosphine. Crystal and molecular structure of tetrachlorobis(triphenylphosphine)tungsten(IV)

Cited by 15 publications

References 4 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

Tungsten(vi) selenide tetrachloride, WSeCl4 – synthesis, properties, coordination complexes and application of [WSeCl4(SenBu2)] for CVD growth of WSe2 thin films

Improved synthetic routes to tungsten(IV) bromide complexes

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Tungsten(vi) selenide tetrachloride, WSeCl₄ – synthesis, properties, coordination complexes and application of [WSeCl₄(SeⁿBu₂)] for CVD growth of WSe₂ thin films