Browse by author
Lookup NU author(s): Dr John ErringtonORCiD, Professor William Clegg, Dr Ross Harrington
Full text for this publication is not currently held within this repository. Alternative links are provided below where available.
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)
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
URL: http://dx.doi.org/10.1002/ejic.200900640
DOI: 10.1002/ejic.200900640
Altmetrics provided by Altmetric