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Interconverting WW Triple Bonds and W4 Clusters: Structures of W4(OPrn)16 and [Li2W2(OPrn)8(DME)]2*

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Abstract

Alcoholysis of W2(NMe2)6 with excess n-propanol in hexane yields the tetranuclear cluster, W4(OPrn, I. Reduction of I with two equivalents of Li2COT in THF gives a small yield of Li2W2(OPrn)8. Single crystals were isolated by cooling the product mixture in DME and were shown to be [Li2W2(OPrn)8(DME)]2, II, which consists of a unique “dimer of dimers” structure. In this reaction sequence, W 16+4 cluster formation is followed by four electron reduction to reform the (W≡W)6+ unit. Better yields of the lithium salt can be obtained by the addition of LiOPrn/HOPrn solutions to W2(OBut)6 in which case Li2W2(OPrn)8 has been obtained as a 1:1 adduct with LiOPr. This identity of this salt was confirmed by solution NMR spectroscopy. In the alternative reaction, the (W≡W)6+ center remains intact from reactant to product. No attempt has been made to separate the product from excess LiOPr. DFT (ADF 2004.01) molecular orbital calculations on the model cluster W4(OH)16 are used to help elucidate the disruption of the W4 cluster upon four electron reduction. The molecular structures of compounds I and II are reported.

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Acknowledgements

This work was supported by the NSF. We thank Dr. Chunhua Yan of the Ohio State University Campus Chemical Instrumentation Center for his assistance in obtaining 600 MHz proton NMR spectra on I. We also thank Dr. Karl Vermillion of the Ohio State University Chemistry Department for assistance in various NMR experiments on II. We are grateful to the Ohio Supercomputing Center for a grant of computational time on the Center of Excellence (COE) Pentium Cluster.

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Authors and Affiliations

  1. Newman and Wolfrom Laboratory of Chemistry, The Ohio State University, 100 W. 18th Avenue, Columbus, OH, 43210, USA

    Malcolm H. Chisholm & Judith C. Gallucci

  2. Department of Chemistry, The Ohio State University at Mansfield, 1680 University Drive, Mansfield, OH, 44906, USA

    Carl B. Hollandsworth

Authors
  1. Malcolm H. Chisholm
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  2. Judith C. Gallucci
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  3. Carl B. Hollandsworth
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Correspondence to Malcolm H. Chisholm.

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*Dedicated to Professor F. A Cotton on the occasion of his 75th birthday.

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Chisholm, M.H., Gallucci, J.C. & Hollandsworth, C.B. Interconverting WW Triple Bonds and W4 Clusters: Structures of W4(OPrn)16 and [Li2W2(OPrn)8(DME)]2*. J Clust Sci 16, 231–249 (2005). https://doi.org/10.1007/s10876-005-4546-0

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  • DOI: https://doi.org/10.1007/s10876-005-4546-0

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