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The synthesis and unexpected solution chemistry of thermochromic carborane-containing osmium half-sandwich complexes
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Pitto-Barry, Anaïs, South, Amy, Rodger, Alison and Barry, Nicolas P. E. (2016) The synthesis and unexpected solution chemistry of thermochromic carborane-containing osmium half-sandwich complexes. Dalton Transactions, 45 (4). 1763-1768 . doi:10.1039/c5dt04398k ISSN 1477-9226.
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Official URL: http://dx.doi.org/10.1039/C5DT04398K
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.
Item Type: | Journal Article | ||||||||||
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Subjects: | Q Science > QD Chemistry | ||||||||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||||||
Library of Congress Subject Headings (LCSH): | Organometallic compounds, Organic compounds, Thermochromism, Chemistry | ||||||||||
Journal or Publication Title: | Dalton Transactions | ||||||||||
Publisher: | Royal Society of Chemistry | ||||||||||
ISSN: | 1477-9226 | ||||||||||
Official Date: | 28 January 2016 | ||||||||||
Dates: |
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Volume: | 45 | ||||||||||
Number: | 4 | ||||||||||
Page Range: | 1763-1768 | ||||||||||
DOI: | 10.1039/c5dt04398k | ||||||||||
Status: | Peer Reviewed | ||||||||||
Publication Status: | Published | ||||||||||
Access rights to Published version: | Open Access (Creative Commons) | ||||||||||
Date of first compliant deposit: | 13 January 2016 | ||||||||||
Date of first compliant Open Access: | 13 January 2016 | ||||||||||
Funder: | Leverhulme Trust (LT), University of Warwick | ||||||||||
Grant number: | ECF-2013-414 to NPEB , RD14102 to NPEB |
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