Toggle Main Menu Toggle Search

Open Access padlockePrints

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

Lookup NU author(s): Dr John Errington, Emeritus Professor Bill Clegg, Dr Ross Harrington

Downloads

Full text for this publication is not currently held within this repository. Alternative links are provided below where available.


Abstract

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

URL: http://dx.doi.org/10.1002/ejic.200900640

DOI: 10.1002/ejic.200900640


Altmetrics

Altmetrics provided by Altmetric


Actions

Find at Newcastle University icon    Link to this publication


Share