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

Davis, Martin F.; Jura, Marek; Leung, Alethea; Levason, William; Littlefield, Benjamin T. R.; Reid, Gillian; Webster, Michael

doi:10.1039/b811422f

Cited by 26 publications

(28 citation statements)

References 23 publications

(43 reference statements)

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“…VOCl 3 forms complexes with N-and O-donor ligands, and even unstable examples with neutral sulfur ligands [33,34] but with VO 2 Cl, only N-and a limited number of O-donor examples form. [35] This suggests that the presence of two strong π-donor oxido groups significantly reduces the Lewis acidity of the central metal atom, and a similar effect will be present in CrO 2 Cl 2 (CrOCl 4 is unknown, so direct comparisons cannot be made). Adduct formation requires the deformation of the stable tetrahedral CrO 2 Cl 2 arrangement into a four coordinate fragment required in the octahedral adducts, and the energy required for this deformation needs to be recovered from the Lewis acid-base bonds formed.…”

Section: Discussionmentioning

confidence: 99%

“…It is plausible that weaker Cr-OPR 3 [28] The redox chemistry found with soft donor ligands closely resembles that of high valent vanadium species, although the chromium systems are stronger oxidants. [33][34][35] …”

Section: Discussionmentioning

confidence: 99%

“…-is well known. [35] The characterization of the Cr V complexes [CrOCl 3 (diimine)] was also achieved.…”

Section: Discussionmentioning

confidence: 99%

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Synthesis, Properties, and Structures of Chromium(VI) and Chromium(V) Complexes with Heterocyclic Nitrogen Ligands

Levason

Reid

Zhang

2013

Zeitschrift anorg allge chemie

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Abstract. The reaction of CrO 2 Cl 2 with 2,2Ј-bipyridyl or 1,10-phenanthroline (diimine) in CCl 4 or anhydrous CH 3 CO 2 H solution, produces orange-brown diamagnetic [CrO 2 Cl 2 (diimine)]. The X-ray structure of [CrO 2 Cl 2 (2,2Ј-bipy)] shows a six-coordinate central chromium(VI) atom with cis-dioxo groups trans to the diimine. In contrast, the diimines react with CrO 3 in CH 3 CO 2 H / conc. aqueous HCl to form bright red paramagnetic Cr V complexes, [CrOCl 3 (diimine)]. The X-ray structure of [CrOCl 3 (2,2Ј-bipy)] shows a six-coordinate central chromium atom with mer-chlorines and the diimine trans to O/Cl. The

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

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Synthesis, Properties, and Structures of Chromium(VI) and Chromium(V) Complexes with Heterocyclic Nitrogen Ligands

Levason

Reid

Zhang

2013

Zeitschrift anorg allge chemie

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“…No structures of the hydrated dioxovanadium(V) ion have been reported so far in the solid state, but one five-coordinate neutral solvate 29 and a few additional five- and six-coordinate anionic hydrated and solvated complexes have been reported, 30–32 Tables S4a–e. In six-coordinate dioxovanadium(V) complexes the bonds trans to the oxo groups are significantly longer than those in cis position.…”

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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“…57,58,59 Neither VO2F nor VO2Cl form complexes with chalcogenoethers. 60 The thia-macrocycles, [9] 64 The structure of [VOCl2( [9]aneS3)] shows a distorted octahedral geometry at vanadium. 63 The N2S-donor macrocycle, [9]aneN2S, also forms an octahedral complex [VOCl2( [9]aneN2S)], the structure of which shows the S lies trans to V=O (Fig 26).…”

Section: Vanadium(v)mentioning

confidence: 99%

Developments in the chemistry of the hard early metals (Groups 1–6) with thioether, selenoether and telluroether ligands

2016

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The coordination chemistry of neutral thio-, seleno-and telluroether ligands towards the hard s-block, f-block and higher oxidation state early d-block metals has developed significantly over the 15 or so years. This has revealed several hitherto unknown classes of complexes and new insights into the chemistries of these hard-soft metal-ligand combinations. This Perspective describes the synthetic routes used to access such complexes and draws out their key structural features and spectroscopic properties. Where appropriate, applications of these species are also highlighted, including their use as single source precursors for the chemical vapour deposition of semiconducting metal chalcogenide thin films and as pre-catalysts for olefin polymerisation reactions. IntroductionThioether and selenoether ligands, which are neutral sulfur and selenium donors respectively, were for many years viewed as modest σ-donor ligands that formed complexes with the softer later d-block elements in low or medium oxidation states, or with post transition metals such as silver or mercury.1,2Complexes of the early d-block metals were mostly limited to low valent organometallics or carbonyls. The chemistry of telluroethers was very little explored, in major part a reflection of their limited availability and, for the alkyl telluroethers in particular, their extremely malodorous nature. 2,3The R2Te ligands are also oxygen sensitive (in contrast to the air stable R2S or R2Se), modest reducing agents and prone to cleavage of the CTe bond upon reaction with some metal centres. Even today, their chemistry remains much less extensive than that of their lighter analogues. 4 Major developments in the syntheses and coordination chemistry of macrocyclic thioethers considerably extended the range and stability of complexes containing metal centres across the d-block. More recent work has resulted in complexes of chalcogenoethers with many of the p-block elements,

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

Cited by 26 publications

References 23 publications

Synthesis, Properties, and Structures of Chromium(VI) and Chromium(V) Complexes with Heterocyclic Nitrogen Ligands

Synthesis, Properties, and Structures of Chromium(VI) and Chromium(V) Complexes with Heterocyclic Nitrogen Ligands

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

Developments in the chemistry of the hard early metals (Groups 1–6) with thioether, selenoether and telluroether ligands

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