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    The synthesis and unexpected solution chemistry of thermochromic carborane-containing osmium half-sandwich complexes

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    Publication date
    2016
    Author
    Pitto-Barry, Anaïs
    South, A.
    Rodger, A.
    Barry, Nicolas P.E.
    Keyword
    Osmium; Half-sandwich complexes; Solution chemistry
    Rights
    © 2016 The Royal Society of Chemistry. Reproduced in accordance with the publisher's self-archiving policy. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
    Peer-Reviewed
    Yes
    
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    Abstract
    The functionalisation of the 16-electron complex [Os(η6-p-cymene)(1,2-dicarba-closo-dodecarborane- 1,2-dithiolato)] (1) with a series of Lewis bases to give the 18-electron complexes of general formula [Os(η6-p-cymene)(1,2-dicarba-closo-dodecarborane-1,2-dithiolato)(L)] (L = pyridine (2), 4-dimethylaminopyridine (3), 4-cyanopyridine (4), 4-methoxypyridine (5), pyrazine (6), pyridazine (7), 4,4’-bipyridine (8) and triphenylphosphine (9)) is reported. All 18-electron complexes are in equilibrium in solution with the 16-electron precursor, and thermochromic properties are observed in some cases (2, 3, 5, 8, and 9). The binding constants and Gibbs free energies of the equilibria are determined using UV-visible titrations and their stabilities investigated. Synthetic routes for forcing the formation of the 18-electron species are proposed, and analytical methods to characterise the equilibria are described.
    URI
    http://hdl.handle.net/10454/11260
    Version
    Published version
    Citation
    Pitto-Barry A, South A and Rodger A et al (2016) The synthesis and unexpected solution chemistry of thermochromic carborane-containing osmium half-sandwich complexes. Dalton Transactions. 45(4): 1763-1768.
    Link to publisher’s version
    http://dx.doi.org/10.1039/C5DT04398K
    Type
    Article
    Collections
    Life Sciences Publications

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