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Improved synthetic routes to tungsten(IV) bromide complexes

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Abstract

Convenient synthetic routes to the compounds WBr4 (1), WBr4(MeCN)2 (2), WBr4(THF)2 (3), WBr4(PPh3)2 (4), WBr4(bpy) (6), and WBr4(dppe) (7) are described via the solution-phase oxidation of W(CO)6 using two equivalents of bromine. These one-pot syntheses use inexpensive and readily available starting materials and produce analytically pure compounds with high yields under mild conditions. Attempts to grow crystals of 1 by heating in a sealed tube at ~200 °C resulted in formation of the previously reported compound WOBr4. Attempts to recrystallize 4 from dichloromethane solution produced [HPPh3]2[WBr6] (5). X-ray crystallographic studies showed that 5 consists of an array of [WBr6]2− anions and [HPPh3]+ cations and that 7·CH2Cl2 has the expected six-coordinate tungsten center. The synthesis of tungsten(IV) bromide compounds via oxidation of W(CO)6 is simple and provides better yields than previously reported methods. This synthetic route also has many advantages over the syntheses of similar tungsten(IV) chloride compounds which involve reduction of WCl6.

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Acknowledgments

W.R.H. acknowledges the Partnership for Minority Access to Doctoral Degrees program of the National Institutes of Health for financial support. This work was supported by the Donors of the Petroleum Research Fund administered by the American Chemical Society, the Research Corporation (Cottrell College Science Award to S.C.S.), and the North Carolina Space Grant Consortium. The Varian Unity INOVA NMR spectrometer was purchased with funds provided by the US Office of Naval Research.

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Authors and Affiliations

  1. Department of Chemistry, North Carolina Central University, 1801 Fayetteville Street, Durham, NC, 27707, USA

    Mohammad A. I. Bhuiyan, Willie R. Hargrove & Shawn C. Sendlinger

  2. Department of Chemistry and Biochemistry, College of Charleston, 66 George Street, Charleston, SC, 29424, USA

    Clyde R. Metz

  3. Department of Chemistry, University of North Carolina at Chapel Hill, 131 South Road, Chapel Hill, NC, 27599, USA

    Peter S. White

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  1. Mohammad A. I. Bhuiyan
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  2. Willie R. Hargrove
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  3. Clyde R. Metz
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  4. Peter S. White
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  5. Shawn C. Sendlinger
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Correspondence to Shawn C. Sendlinger.

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Bhuiyan, M.A.I., Hargrove, W.R., Metz, C.R. et al. Improved synthetic routes to tungsten(IV) bromide complexes. Transition Met Chem 40, 613–621 (2015). https://doi.org/10.1007/s11243-015-9954-x

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  • DOI: https://doi.org/10.1007/s11243-015-9954-x

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