The reactivity of tungsten hexachloride with tetrahydrofuran and 2-methoxyethanol

Abstract

The ring opening polymerization reaction of tetrahydrofuran (thf) by WCl6 was investigated under different conditions, and the polymeric material was characterized by NMR and SEC (Size Exclusion Chromatography) analyses. The mixed valence complex [(thf)2(μ-H)][WOCl3(thf)2(μ-O)], 3, was isolated from the reactions of WCl6 with 4–8 equivalents of thf in dichloromethane at room temperature, and crystallographically characterized. The formation of 3 was preceded by that of WOCl4(thf), 2, while Cl(CH2)4Cl and Cl(CH2)4O(CH2)4Cl were identified as the prevalent organic side products. The 1:1 M reaction of WCl6 with MeO(CH2)2OH, in CH2Cl2 at room temperature, afforded the complexes (WOCl4)2(μ-κ2-1,4-dioxane), 4, and WCl5(OCH2CH2OMe), 5, in admixture with Cl(CH2)2Cl, MeO(CH2)2OMe and MeCl. Also complex 4, resulting from a [Formula presented] bond forming process, was characterized by X-ray crystallography

Pentagonal bipyramidal complexes of WOCl4 and WSCl4 with diphosphine and diarsine ligands

“…Tungsten(VI) oxide tetrachloride, WOCl4, and tungsten(VI) sulfide tetrachloride, WSCl4, are moderate Lewis acids [1][2][3] and form, in addition to the corresponding anions [WOCl5]and [WSCl5] - [4,5], complexes with a range of hard, neutral N-and O-donor ligands. These include [WOCl4(RCN)] (R = Me, Et, Ph) [6,7], [WOCl4(thf)] [6,8], [WOCl4(Me4urea)] [9], [WOCl4(OPPh3)n] (n = 1 or 2) [10],…”

Tungsten–Ligand Bond Strengths for 2p Elements Including σ- and π-Bond Strength Components, A Density Functional Theory and ab Initio Study

“…Much of the research effort in catalysis using Earth-abundant metals has focused on 3d metals; however, not all heavy transition metals are precious. Those of the early 4d and 5d series are “green” in both an economic and ecological sense, Figure . − Additionally, in the activation of light alkanes, the generally stronger metal–C and metal–H bond strengths for 4d and 5d metal complexes versus their 3d congeners can mitigate the thermodynamic, and hence kinetic, impediments to nonradical methane activation that often arise due to weak M 3d –C/H bonds …”

Synthesis and Structural Characterization of Non‐Homoleptic Carbamato Complexes of VV and WVI and Their Facile Implantation onto Silica Surfaces

“…The latter anion is a distorted octahedral W VI complex, containing one oxido and one amido NEt 2 ligand in the cis position, as well as four chloride ligands. The W(1)–O(1) [1.703(2) Å] interaction is typical for a W=O double bond and shows a strong trans effect. Thus, the trans W(1)–Cl(3) bond [2.5766(7) Å] is considerably elongated, compared with W(1)–Cl(1) [2.3709(7) Å] and W(1)–Cl(2) [2.3603(7) Å], which are in mutual trans positions.…”