Pentaaquaoxovanadium(IV) bis(trifluoromethanesulfonate)

Magnussen, Magnus; Brock‐Nannestad, Theis; Bendix, Jesper

doi:10.1107/s010827010605219x

Cited by 8 publications

(10 citation statements)

References 13 publications

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“…The triflate anion does not directly interact with the cation and only forms hydrogen bonds with the water molecules in the primary hydration shell. This propensity of triflate to interact with the cations through their hydration shell has also been observed for triflate interacting with protons using static and dynamic ab initio studies , as well as crystallographic and NMR studies of vanadium cations with the triflate as the counterion. ,,,, Hence, the triflate ion has the least effect on the destabilization of the hydrated vanadium cations and may serve as a stabilizing agent similar to methanesulfonic acid (CH 3 SO 3 H) which has already been shown to stabilize VRFB electrolytes …”

Section: Resultsmentioning

confidence: 71%

Effect of Sulfuric and Triflic Acids on the Hydration of Vanadium Cations: An ab Initio Study

Sepehr

Paddison

2015

J. Phys. Chem. A

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Vanadium redox flow batteries (VRFBs) may be a promising solution for large-scale energy storage applications, but the crossover of any of the redox active species V(2+), V(3+), VO(2+), and VO2(+) through the ion exchange membrane will result in self-discharge of the battery. Hence, a molecular level understanding of the states of vanadium cations in the highly acidic environment of a VRFB is needed. We examine the effects of sulfuric and triflic (CF3SO3H) acids on the hydration of vanadium species as they mimic the electrolyte and functional group of perfluorosulfonic acid (PFSA) membranes. Hybrid density functional theory in conjunction with a continuum solvation model was utilized to obtain the local structures of the hydrated vanadium cations in proximity to H2SO4, CF3SO3H, and their conjugate anions. The results indicate that none of these species covalently bond to the vanadium cations. The hydration structure of V(3+) is more distorted than that of V(2+) in an acidic medium. The oxo-group of VO2(+) is protonated by either acid, in contrast to VO(2+) which is not protonated. The atomic partial charge of the four oxidation states of vanadium varies from +1.7 to +2.0. These results provide the local solvation structures of vanadium cations in the VRFBs environment that are directly related to the electrolytes stability and diffusion of vanadium ions into the membrane.

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Section: Resultsmentioning

confidence: 71%

Effect of Sulfuric and Triflic Acids on the Hydration of Vanadium Cations: An ab Initio Study

Sepehr

Paddison

2015

J. Phys. Chem. A

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“…39i The reported structure, crystallizing in space group P 2 1 /m (No. 11), is confirmed in this study with near-identical structure parameters, Table 2 and Figure S2.…”

Section: Resultsmentioning

confidence: 99%

“…They all feature four near-perpendicularly bound waters, mean d V-O = 2.024 Å, and a fifth water molecule in trans position to the V=O bond more weakly bound, mean d V-O = 2.189 Å, forming a distorted octahedral structure, 39 Table S3a. Additionally, four dmso and urea solvates of oxovanadium(IV) display a very similar coordination pattern as the hydrates with mean bond distances 1.583, 2.022, and 2.183 Å, 40 respectively, Table S3b.…”

Section: Introductionmentioning

confidence: 99%

A Coordination Chemistry Study of Hydrated and Solvated Cationic Vanadium Ions in Oxidation States +III, +IV, and +V in Solution and Solid State

2012

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The coordination chemistry of hydrated and solvated vanadium(III), oxovanadium(IV), and dioxovanadium(V) ions in the oxygen donor solvents water, dimethylsulfoxide (dmso) and N,N′-dimethylpropyleneurea (dmpu) has been studied in solution by EXAFS and large angle X-ray scattering (LAXS) and in solid state by single crystal X-ray diffraction and EXAFS. The hydrated vanadium(III) ion has a regular octahedral configuration with a mean V-O bond distance of 1.99 Å. In the hydrated and dimethylsulfoxide solvated oxovanadium(IV) ions vanadium binds strongly to an oxo group at ca. 1.6 Å. The solvent molecule trans to the oxo group is very weakly bound, at ca. 2.2 Å, while the remaining four solvent molecules, with a mean V-O bond distance of 2.0 Å, form a plane slightly below the vanadium atom; the mean O=V-Operp bond angle is ca. 98°. In the dmpu solvated oxovanadium(IV) ion, the space demanding properties of the dmpu molecule leaving no solvent molecule in the trans position to the oxo group which reduces the coordination number to 5. The O=V-O bond angle is consequently much larger, 106°, and the mean V=O and V-O bond distances decrease to 1.58 and 1.97 Å, respectively. The hydrated and dimethylsulfoxide solvated dioxovanadium(V) ions display a very distorted octahedral configuration with the oxo groups in cis position with mean V=O bond distances of 1.6 Å and a O=V=O bond angle of ca. 105°. The solvent molecules trans to the oxo groups are weakly bound, at ca. 2.2 Å, while the remaining two have bond distances of 2.02 Å. The experimental studies of the coordination chemistry of hydrated and solvated vanadium(III,IV,V) ions are complemented by summarizing previously reported crystal structures to yield a comprehensive description of the coordination chemistry of vanadium with oxygen donor ligands.

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“…The mean planes of adjacent acridine moieties are either parallel (remain at an angle of 0.0 (1)°) or inclined at an angle of 35.6 (1)°. The trifluoromethanesulfonate anions are disordered over two positions with site occupancy factors of 0.591 (8) and 0.409 (8) [similar disorder was found in pentaaquaoxovanadium(IV)bis(trifluoromethanesulfonate) (Magnussen et al, 2007)]. (Takahashi et al, 2001), like the C-F•••π (Dorn et al, 2005) and S-O•••π (Dorn et al, 2005) interactions.…”

Section: Tablementioning

confidence: 73%

“…For general background to chemiluminescence, see: Sato (1996); Wró blewska et al (2004); Zomer & Jacquemijns (2001). For related structures, see: Huta et al (2002); Magnussen et al (2007); Stowell et al (1991); Toma et al (1994); Trzybiń ski et al (2010); Zadykowicz et al (2009a,b). For intermolecular interactions, see: Aakerö y et al (1992); Dorn et al (2005); Novoa et al (2006); Takahashi et al (2001).…”

Section: Related Literaturementioning

confidence: 99%

9-Phenyl-10H-acridinium trifluoromethanesulfonate

et al. 2010

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In the crystal structure of the title compound, C19H14N+·CF3SO3 −, the cations are linked to each other by very weak C—H⋯π interactions, while the cations and anions are connected by N—H⋯O, C—H⋯O and S—O⋯π interactions. The acridine ring system and the phenyl ring are oriented at an angle of 80.1 (1)° with respect to each other. The mean planes of adjacent acridine units are either parallel or inclined at an angle of 35.6 (1)°. The trifluoromethanesulfonate anions are disordered over two positions; the site occupancy factors are 0.591 (8) and 0.409 (8).

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Pentaaquaoxovanadium(IV) bis(trifluoromethanesulfonate)

Cited by 8 publications

References 13 publications

Effect of Sulfuric and Triflic Acids on the Hydration of Vanadium Cations: An ab Initio Study

Effect of Sulfuric and Triflic Acids on the Hydration of Vanadium Cations: An ab Initio Study

A Coordination Chemistry Study of Hydrated and Solvated Cationic Vanadium Ions in Oxidation States +III, +IV, and +V in Solution and Solid State

9-Phenyl-10H-acridinium trifluoromethanesulfonate

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