Substitution and redox reactions involving vanadium oxotrifluorine

Kolta, G.A.; Sharp, D. W. A.; Winfield, John M.

doi:10.1016/s0022-1139(00)82883-3

Cited by 9 publications

(10 citation statements)

References 20 publications

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“…The solid is moisture-sensitive, turns brown on exposure to air, decomposes in MeCN solution in a few days, and turns green, although the pure dry solid can be kept for weeks without decomposition. The composition approximates to [VOF 3 (MeCN)], but as previously observed, [13] it is sometimes rather deficient in nitrile. The IR spectrum shows one strong υ(CN) mode at 2335 cm -1 , a strong combination band υ(CC) + δ(CH 3 ) at 2297 cm -1 , υ(VO) at 1029 cm -1 and several υ(VF) modes at 720-583 cm -1 .…”

Section: Resultssupporting

confidence: 69%

“…[9] The oxide trifluoride, VOF 3 , is a yellow solid which, unlike the molecular (C 3v ) VOCl 3 and VOBr 3 , is polymeric with a dinuclear OF 2 V(µ-F) 2 VOF 2 core linked by long Fbridges into a polymer with distorted six-coordinate vanadium centres. [10] Its coordination chemistry with neutral ligands is little explored, [11][12][13] and none of the few reported complexes have been studied in any detail. There is a large amount of work on the oxidofluoridovanadates(V) including [VO 2 -, which are known as mononuclear species with large organic cations, but in the alkali-metal salts are often fluoride-bridged oligomers.…”

Section: Introductionmentioning

confidence: 99%

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Complexes of Vanadium(V) Oxide Trifluoride with Nitrogen and Oxygen Donor Ligands: Coordination Chemistry and Some Fluorination Reactions

et al. 2008

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Abstract[VOF3(MeCN)], obtained by dissolving VOF3 in dry acetonitrile, is a useful synthon for the preparation of complexes of the oxide‐fluoride, and the reaction with 2,2′‐bipyridyl, 1,10‐phenanthroline, Me2N(CH2)2NMe2 and Ph2P(O)CH2P(O)Ph2 (L–L), or Ph3PO, Me3PO, Ph3AsO, pyridine and pyridine N‐oxide (L), produces the complexes [VOF3(L–L)] or [VOF3(L)2] respectively. These were characterised by microanalysis, IR, UV/Vis and multinuclear NMR [51V, 19F{1H}, 31P{1H}, 1H] spectroscopy, the data showing them to besix‐coordinate with trans F–V–F units and the neutralligands trans to O and F, respectively. X‐ray crystal structures of [VOF3(1,10‐phenanthroline)], [VOF3(Ph3PO)2] and [VOF3(pyNO)2] confirm the geometry, although the first two exhibit O/F disorder trans to the neutral ligand. Unstable complexes with ether and thioether ligands including [VOF3{MeO(CH2)2OMe}], [VOF3{MeS(CH2)2SMe}] and [VOF3(15‐crown‐5)] are also described; these decompose rapidly even in the solid state, with fluorination of the ligands. The [VOF3(Ph3AsO)2] also decomposes in solutionto a mixture of products including Ph3AsF2 and [V6O12F4(Ph3AsO)2(Ph2AsO2)2] identified crystallographically. Comparisons with complexes of VOCl3 are also described.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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Section: Resultssupporting

confidence: 69%

Section: Introductionmentioning

confidence: 99%

Complexes of Vanadium(V) Oxide Trifluoride with Nitrogen and Oxygen Donor Ligands: Coordination Chemistry and Some Fluorination Reactions

et al. 2008

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“…was made from VOF 3 and (Me 3 Si) 2 O in anhydrous MeCN as described by Kolta et al 16 The orange product is obtained in near quantitative yield, and the spectroscopic data are as reported. 8,16…”

Section: Vo 2 Fmentioning

confidence: 99%

“…Copies of these data can be obtained free of charge from the Cambridge Crystallographic Data Centre. †Results and discussionPreparation of VO 2 X (X = F or Cl)The reaction of VOF 3 with hexamethyldisiloxane, (Me 3 Si) 2 O, in MeCN solution at room temperature results in precipitation of VO 2 F in near quantitative yield 16. The orange-brown VO 2 F is insoluble in MeCN, thf, chlorocarbons, MeO(CH 2 ) 2 OMe, dmf or acetone.…”

mentioning

confidence: 99%

Synthesis, chemistry and structures of complexes of the dioxovanadium(v) halides VO2F and VO2Cl

et al. 2008

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[VO2F(L-L)] (L-L = 2,2'-bipyridyl, 1,10-phenanthroline, Me2N(CH2)2NMe2) and [VO2F(py)2] (py = pyridine) have been prepared from the corresponding [VOF3(L-L)] or [VOF3(py)2] and O(SiMe3)2 in MeCN solution. VO2F (itself made from VOF3 and O(SiMe3)2 in MeCN) forms [Me4N][VO2F2] with [Me4N]F, but does not react with neutral N- or O-donor ligands. VO2Cl, prepared from VOCl3 and ozone, reacts with 2,2'-bipyridyl or 1,10-phenanthroline to form [VO2Cl(L-L)], with pyridine or pyridine-N-oxide (L) to produce [VO2Cl(L)2], and with OPPh3 or OAsPh3 (L') gives [VO2Cl(L')]. A second product from the OPPh3 system is the ionic [VO2(OPPh3)3][VO2Cl2] containing a trigonal bipyramidal cation. Neither VO2F nor VO2Cl form isolable complexes with MeCN, thf or MeO(CH2)2OMe, and both are reduced by P-, As-, S- or Se-donor ligands. [Ph4As][VO2X2] (X = F or Cl) react with 2,2'-bipyridyl to form [VO2X(2,2'-bipyridyl)], but similar reactions with weaker O-donor ligands fail. The complexes have been characterised by IR, multinuclear NMR (1H, 19F, 51V or 31P) and UV-visible spectroscopy. X-ray crystal structures are reported for [VO2F(py)2], [VO2Cl(L)2] (L = py or pyNO) and [VO2(OPPh3)3][VO2Cl2].

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“…VOF3 is the only commercially available material, which is extremely sensitive to air and moisture and easy to decompose through hydrolysis. In an earlier work 38 , an orange-yellow powder VO2F was identified by reaction of VOF3 with Me3SiOSiMe3 in acetonitrile under an inert atmosphere. However, the structure and applications of VO2F were unexplored over decades.…”

Section: Introductionmentioning

confidence: 99%

Lithiation-driven structural transition of VO₂F into disordered rock-salt Li_xVO₂F

et al. 2016

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We synthesize a new vanadium oxyfluoride VO2F (rhombohedral, R3,¯ c) through a simple one-step ball-milling route and demonstrate its promising lithium storage properties with a high theoretical capacity of 526 mAh g -1 . Similar to V2O5, VO2F transfers into active disordered rock-salt (Fm3,¯ m) phase after initial cycling against lithium anode, as confirmed by diffraction and spectroscopic experiments. The newly formed nanosized LixVO2F remains its crystal structure over further cycling between 4.1 and 1.3 V. A high capacity of 350 mAh g -1 at 2.5 V was observed at 25°C and 50 mA g -1 . Furthermore, superior performance was observed for VO2F in comparison with a commercial crystalline V2O5, in terms of discharge voltage, voltage hysteresis and reversible capacity.

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Substitution and redox reactions involving vanadium oxotrifluorine

Cited by 9 publications

References 20 publications

Complexes of Vanadium(V) Oxide Trifluoride with Nitrogen and Oxygen Donor Ligands: Coordination Chemistry and Some Fluorination Reactions

Complexes of Vanadium(V) Oxide Trifluoride with Nitrogen and Oxygen Donor Ligands: Coordination Chemistry and Some Fluorination Reactions

Synthesis, chemistry and structures of complexes of the dioxovanadium(v) halides VO2F and VO2Cl

Lithiation-driven structural transition of VO₂F into disordered rock-salt Li_xVO₂F

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Substitution and redox reactions involving vanadium oxotrifluorine

Cited by 9 publications

References 20 publications

Complexes of Vanadium(V) Oxide Trifluoride with Nitrogen and Oxygen Donor Ligands: Coordination Chemistry and Some Fluorination Reactions

Complexes of Vanadium(V) Oxide Trifluoride with Nitrogen and Oxygen Donor Ligands: Coordination Chemistry and Some Fluorination Reactions

Synthesis, chemistry and structures of complexes of the dioxovanadium(v) halides VO2F and VO2Cl

Lithiation-driven structural transition of VO2F into disordered rock-salt LixVO2F

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Lithiation-driven structural transition of VO₂F into disordered rock-salt Li_xVO₂F