Complexes of WOCl4 and WSCl4 with neutral N- and O-donor ligands: Synthesis, spectroscopy and structures

Victoria K Greenacre,Andrew L Hector,William Levason,Gillian Reid,Danielle E Smith,Laura Sutcliffe

doi:10.1016/j.poly.2019.01.044

Victoria K Greenacre, Andrew L Hector + Show 4 more

Open Access

https://doi.org/10.1016/j.poly.2019.01.044

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Abstract

The complexes [WOCl4(L)] and [WSCl4(L)] (L = OPPh3, OPMe3, pyridine, 2,2′-bipyridyl), [{WOCl4}2(µ-L-L)] and [{WSCl4}2(µ-L-L)] (L-L = Ph2P(O)(CH2)nP(O)Ph2 (n = 1, 2)) have been prepared from WOCl4 or WSCl4 and the ligands in anhydrous CH2Cl2 solution, and characterised by microanalysis, IR and NMR (1H, 31P{1H}) spectroscopy. X-Ray crystal structures are reported for [WOCl4(OPPh3)], [{WOCl4}2(µ-Ph2P(O)(CH2)P(O)Ph2)] and [{WSCl4}2(µ-Ph2P(O)(CH2)2P(O)Ph2)]. All, except those of 2,2′-bipyridyl, are six-coordinate with the neutral donor trans to WO or WS. Spectroscopic data suggest that the [WOCl4(2,2′-bipy)] and [WSCl4(2,2′-bipy)] are seven-coordinate. Comparison of the structural and spectroscopic data for the two series of complexes indicate little difference in Lewis acidity between the two tungsten(VI) moieties. Decomposition of [WOCl4(OPMe3)] in solution gave the cyclic trimer [W3O3(µ-O)3Cl6(OPMe3)3], the structure of which revealed a six-membered W3O3 ring core with very asymmetric oxido-bridges. The structure of the tungsten(V) complex [WOCl3(2,2′-bipy)] is also reported.

Highlights

The oxide and sulfide halides of the early d-block metals in their higher oxidation states are Lewis acidic and form complexes with a variety of neutral ligands [1]
We report here a comparison of the complexes of WOCl4 and WSCl4 with a series of neutral N- and O-donor ligands
The complexes were subsequently synthesised by reaction of the appropriate ligand with the WECl4 (E = O or S) in anhydrous CH2Cl2

Summary

Introduction

The oxide and sulfide halides of the early d-block metals in their higher oxidation states are Lewis acidic and form complexes with a variety of neutral ligands [1]. Some corresponding tungsten(VI) sulfide tetrachloride complexes, including [WSCl4(L)] (L = thf, py, RCN), [{WSCl4}2(μ-1,4-dioxane)] and [(WSCl4)2(μ-MeS(CH2)2SMe)] have been prepared, but appear to be less stable than those of WOCl4 [1,5,19,20]. Possible applications of complexes of metal sulfide halides include their use as reagents for the chemical vapour deposition of the layered metal dichalcogenide thin film materials [21,22]. We report here a comparison of the complexes of WOCl4 and WSCl4 with a series of neutral N- and O-donor ligands

Results and Discussion

Conclusions

Experimental