Characterization of the adducts WF6·py and WF6·2py (py = pyridine): crystal structure of WF6·2py

Arnaudet, L.; Bougon, R.; Ban, Buu; Lance, M.; Nierlich, Martine; Thuéry, Pierre; Vigner, Julien

doi:10.1016/0022-1139(94)03160-2

Cited by 14 publications

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“…[9][10][11][12][13][14][15][16][17] Well-documented examples including [WF 6 (2-F-py)] (capped trigonal prism), 13 [WF 6 (py) 2 ] (bicapped trigonal prism), 14 [WF 6 (2,2 0 -bipy)] (structure unknown) 16 and the [WF 4 (2,2 0 -bipy) 2 ] 2+ cation (distorted dodecahedron). 15,16 On the other hand, reaction of WF 6 with sulfite esters, (RO) 2 SO (R = alkyl), or phosphites, (RO) 3 P, result in OR/F exchange to give, for example, [WF 5 (OR)], 12,18 while reaction of WF 6 with OMe 2 causes O/F exchange, forming [WOF 4 (OMe 2 )]. 12 Similar chemistry has been further developed and exploited to provide a useful entry into WOF 4 chemistry, by reaction of WF 6 with (Me 3 Si) 2 O in MeCN solution to form [WOF 4 (MeCN)], from which the MeCN is easily displaced by other neutral ligands.…”

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confidence: 99%

“…The 19 13,14 The IR spectra have very broad strong features at 610 (R = Me) and 622 cm À1 (R = Et), assigned to overlapping W-F stretches. The UV/visible spectrum of [WF 6 (AsMe 3 )] shows a very broad absorption at B22 700 cm À1 , which accounts for the orange-red colour and may be assigned as a ligand to metal charge transfer, As(s) -W(d), since the F(p) -W(d) transitions are expected to lie in the far-UV region.…”

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Neutral and cationic tungsten(vi) fluoride complexes with tertiary phosphine and arsine coordination

et al. 2018

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Reaction of WF6 with AsR3 (R = Me or Et) in anhydrous CH2Cl2 at low temperature forms the neutral seven-coordinate, [WF6(AsR3)] (R = Me, Et), the first arsine complexes of WF6, whilst o-C6H4(EMe2)2 (E = P, As) produces [WF4{o-C6H4(EMe2)2}2][WF7]2. Crystal structures show the latter contain dodecahedral cations, and present the highest oxidation state metal fluoride complexes known (and the highest possible for tungsten) with soft neutral phosphine and arsine coordination.

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Neutral and cationic tungsten(vi) fluoride complexes with tertiary phosphine and arsine coordination

et al. 2018

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“…679) is consistent with octacoordinate W VI complexes such as WF 6 (NC 5 H 5 ) 2 (exptl. 661, [34] calcd. 673 [12] ), WF 6 (L) (L = 2,2'-bipy, 1,10-phen;e xptl.…”

Section: Molecular Structuresmentioning

confidence: 99%

“…1013) to as imilar extent as in WF 6 (NC 5 H 5 )( exptl. 1024, [22,34] calcd. 1041 [22] )a nd WF 6 (NC 5 H 5 ) 2 (exptl.…”

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Stabilisation of [WF₅]⁺ and WF₅ by Pyridine: Facile Access to [WF₅(NC₅H₅)₃]⁺ and WF₅(NC₅H₅)₂

Turnbull

Hazendonk

Wetmore

et al. 2020

Chemistry A European J

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The enhanced reactivity of [WF 5 ] + over WF 6 has been exploited to access an eutrald erivative of elusive WF 5 . The reactiono fW F 6 (NC 5 H 5 ) 2 with [(CH 3 ) 3 Si(NC 5 H 5 )][O 3 SCF 3 ]i n CH 2 Cl 2 results in quantitative formation of trigonal-dodecahedral [WF 5 (NC 5 H 5 ) 3 ] + ,w hich has been characterised as its [O 3 SCF 3 ] À salt by Ramans pectroscopy in the solid state and variable-temperature NMR spectroscopy in solution.T he salt is susceptible to slow decomposition in solution at ambient temperature via dissociation of ap yridyl ligand, and the resultant [WF 5 (NC 5 H 5 ) 2 ] + is reduced to WF 5 (NC 5 H 5 ) 2 in the presence of excess C 5 H 5 N, as determined by 19 FNMR spectrosco-py.P entagonal-bipyramidal WF 5 (NC 5 H 5 ) 2 was isolateda nd characterised by X-ray crystallography and Raman spectroscopy in the solid state, representing the first unambiguously characterised WF 5 adduct, as well as the first heptacoordinate adduct of at ransition-metal pentafluoride. DFT-B3LYP methodsh ave been used to investigatet he reduction of [WF 5 (NC 5 H 5 ) 2 ] + to WF 5 (NC 5 H 5 ) 2 ,s upporting at wo-electron reductiono fW VI to W IV by nucleophilic attack and diprotonation of ap yridyl ligand in the presence of free C 5 H 5 N, followed by comproportionation to W V .

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Stabilization of [WF₅]⁺ by Bidentate N‐Donor Ligands

2019

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Transition‐metal hexafluorides do not exhibit fluoride‐ion donor properties in the absence of donor ligands. We report the first synthesis of donor‐stabilized [MF5]+ derived from a transition‐metal hexafluoride via fluoride‐ion abstraction using WF6(L) (L=2,2′‐bipy, 1,10‐phen) and SbF5(OSO) in SO2. The [WF5(L)][Sb2F11] salts and [WF5(1,10‐phen)][SbF6]⋅SO2 have been characterized by X‐ray crystallography, Raman spectroscopy, and multinuclear NMR spectroscopy. The reaction of WF6(2,2′‐bipy) with an equimolar amount of SbF5(OSO) reveals an equilibrium between [WF5(2,2′‐bipy)]+ and the [WF4(2,2′‐bipy)2]2+ dication, as determined by 19F NMR spectroscopy. The geometries of the cations in the solid state are reproduced by gas‐phase geometry optimizations (DFT‐B3LYP), and NBO analyses reveal that the positive charges of the cations are stabilized primarily by compensatory σ‐electron donation from the N‐donor ligands.

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Characterization of the adducts WF6·py and WF6·2py (py = pyridine): crystal structure of WF6·2py

Cited by 14 publications

References 9 publications

Neutral and cationic tungsten(vi) fluoride complexes with tertiary phosphine and arsine coordination

Neutral and cationic tungsten(vi) fluoride complexes with tertiary phosphine and arsine coordination

Stabilisation of [WF₅]⁺ and WF₅ by Pyridine: Facile Access to [WF₅(NC₅H₅)₃]⁺ and WF₅(NC₅H₅)₂

Stabilization of [WF₅]⁺ by Bidentate N‐Donor Ligands

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Characterization of the adducts WF6·py and WF6·2py (py = pyridine): crystal structure of WF6·2py

Cited by 14 publications

References 9 publications

Neutral and cationic tungsten(vi) fluoride complexes with tertiary phosphine and arsine coordination

Neutral and cationic tungsten(vi) fluoride complexes with tertiary phosphine and arsine coordination

Stabilisation of [WF5]+ and WF5 by Pyridine: Facile Access to [WF5(NC5H5)3]+ and WF5(NC5H5)2

Stabilization of [WF5]+ by Bidentate N‐Donor Ligands

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Stabilisation of [WF₅]⁺ and WF₅ by Pyridine: Facile Access to [WF₅(NC₅H₅)₃]⁺ and WF₅(NC₅H₅)₂

Stabilization of [WF₅]⁺ by Bidentate N‐Donor Ligands