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

Anaïs Pitto-Barry, Amy South, Alison Rodger, Nicolas P E Barry*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

5 Citations (Scopus)
18 Downloads (Pure)

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.

Original languageEnglish
Pages (from-to)1763-1768
Number of pages6
JournalDalton Transactions
Volume45
Issue number4
DOIs
Publication statusPublished - 28 Jan 2016
Externally publishedYes

Bibliographical note

Copyright the Publisher 2016. Version archived for private and non-commercial use with the permission of the author/s and according to publisher conditions. For further rights please contact the publisher.

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