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Issue 4, 2016
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The synthesis and unexpected solution chemistry of thermochromic carborane-containing osmium half-sandwich complexes

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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.

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

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The article was received on 06 Nov 2015, accepted on 11 Dec 2015 and first published on 24 Dec 2015


Article type: Paper
DOI: 10.1039/C5DT04398K
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Dalton Trans., 2016,45, 1763-1768
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    The synthesis and unexpected solution chemistry of thermochromic carborane-containing osmium half-sandwich complexes

    A. Pitto-Barry, A. South, A. Rodger and N. P. E. Barry, Dalton Trans., 2016, 45, 1763
    DOI: 10.1039/C5DT04398K

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