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The synthesis and unexpected solution chemistry of thermochromic carborane-containing osmium half-sandwich complexes
Pitto-Barry, Anaïs South, A. Rodger, A. Barry, Nicolas P.E.
Pitto-Barry, Anaïs
South, A.
Rodger, A.
Barry, Nicolas P.E.
Publication Date
2016
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© 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.
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2015-12-11
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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.
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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.
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Article