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Extending the Lindqvist Family to Late 3d Transition Metals: A Rational Entry to CoW5 Hexametalate Chemistry

Lookup NU author(s): Dr John ErringtonORCiD, Emeritus Professor Bill CleggORCiD, Dr Ross Harrington


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The dimeric CoW5 Lindqvist-type anion [(CoW5O18H)(2)](6-) (1) has been obtained as a tetrabutylammonium (TBA) salt by addition of either [Co(MeCN)(4)(H2O)(2)](2+), or CoCl2 to a "virtual" W5O186- precursor generated by non-aqueous hydrolysis of a mixture of (TBA)(2)WO4 and WO(OMe)(4). Analysis of the X-ray crystal structure of (TBA)(7)1(BF4) by using the Bond Valence Sum (BVS) method reveals that cobalt is present as Co-II and that two protons are associated with CoOW bridging oxygen atoms, one of which is located in a hydrogen bond between the two COW5O18 units, whereas the other is disordered between an adjacent oxygen atom and its symmetry-related site on the other CoW5O18 unit. Treatment with pyridine cleaves dimer 1 to give [(py)CoW5O18H](3-) (2), and the single protonated CoOW site was identified by BVS analysis of an X-ray crystal structure. Due to the higher anionic charge of [CoW5O18](4-), bands due to terminal V-W=O in the FTIR spectra of 1 and 2 are shifted to lower wavenumbers (933 and 935 cm(-1), respectively) compared to those of [W6O19](2-) (974 cm(-1)) and group 4 derivatives [(X)MW5O18](3-)(945-955 cm(-1)), despite protonation of the oxometalate framework. Peaks due to CoW5 oxometalates dominate the electrospray ionisation mass spectra of (TBA)(7)1(BF4) and (TBA)(3)2, the most intense being assigned to {CoW5O17}(2-), which is formally derived from [CoW5O18H](3-) by protonation and loss of H2O. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Publication metadata

Author(s): Errington RJ, Harle G, Clegg W, Harrington RW

Publication type: Article

Publication status: Published

Journal: European Journal of Inorganic Chemistry

Year: 2009

Volume: 2009

Issue: 34

Pages: 5240-5246

ISSN (print): 1434-1948

ISSN (electronic): 1099-0682

Publisher: European Journal of Inorganic Chemistry


DOI: 10.1002/ejic.200900640


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Funder referenceFunder name
Davy Process Technology
EP/F036376X/1UK Engineering and Physical Sciences Research Council