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Thermochromic organometallic complexes: experimental and theoretical studies of 16- to 18-electron interconversions of adducts of arene Ru(ii) carboranes with aromatic amine ligands
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Barry, Nicolas P. E., Deeth, Robert J., Clarkson, Guy J., Prokes, Ivan and Sadler, P. J. (2013) Thermochromic organometallic complexes: experimental and theoretical studies of 16- to 18-electron interconversions of adducts of arene Ru(ii) carboranes with aromatic amine ligands. Dalton Transactions, Volume 42 (Number 7). pp. 2580-2587. doi:10.1039/c2dt32650g
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Official URL: http://dx.doi.org/10.1039/C2DT32650G
Abstract
A series of 18-electron complexes of general formula [Ru(p-cym)(1,2-dicarba-closo-dodecaborane-1,2-dithiolato)(L)] (p-cym = para-cymene; L = 4-dimethylaminopyridine (2), nicotinamide (3), 3-ethynylpyridine (4), N-methylimidazole (5), 4-cyanopyridine (6), and pyridine (7)) were synthesised by reactions between the 16-electron precursor [Ru(p-cym)(1,2-dicarba-closo-dodecaborane-1,2-dithiolato)] (1) and corresponding heterocyclic bases. X-ray crystal structures of complexes 2 and 5 were determined. In dichloromethane and chloroform solutions at ambient temperature, the 18-electron complexes 2–7 are in equilibrium with the 16-electron precursor 1. Each equilibrium is displaced towards the formation of the blue 16-electron or yellow 18-electron complex by increasing or decreasing the temperature of the solution, respectively, which results in controlled and reversible thermochromism. Binding constants (K) and Gibbs free energies (ΔG°) of the six equilibria have been determined by a combination of experiments (Job plots, UV-visible titrations, NMR studies) and also by computation (time-dependent density functional theory, TD-DFT). A linear free energy relationship for log K versus pKa for the pyridine and imidazole ligands was established. The predicted strong interactions of 1 with other aromatic amine ligands, such as amphetamine derivatives, were verified experimentally. This appears to be the first report of reversible 16/18-electron interconversions with associated thermochromic properties for a well-known family of complexes.
| Item Type: | Journal Article | ||||
|---|---|---|---|---|---|
| Divisions: | Faculty of Science > Chemistry | ||||
| Journal or Publication Title: | Dalton Transactions | ||||
| Publisher: | Royal Society of Chemistry | ||||
| ISSN: | 1477-9226 | ||||
| Official Date: | 6 December 2013 | ||||
| Dates: |
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| Volume: | Volume 42 | ||||
| Number: | Number 7 | ||||
| Page Range: | pp. 2580-2587 | ||||
| DOI: | 10.1039/c2dt32650g | ||||
| Status: | Peer Reviewed | ||||
| Publication Status: | Published | ||||
| Access rights to Published version: | Restricted or Subscription Access |
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