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Osmium(II) and ruthenium(II) arene maltolato complexes : rapid hydrolysis and nucleobase binding
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Peacock, Anna F. A., Melchart, Michael, Deeth, Robert J., Habtemariam, Abraha, Parsons, Simon and Sadler, P. J. (2007) Osmium(II) and ruthenium(II) arene maltolato complexes : rapid hydrolysis and nucleobase binding. Chemistry : A European Journal, Volume 13 (Number 9). pp. 2601-2613. doi:10.1002/chem.200601152 ISSN 0947-6539.
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Official URL: http://dx.doi.org/10.1002/chem.200601152
Abstract
Density functional calculations show that aquation of [Os(eta(6)-arene)(XY)Cl](n+) complexes is more facile for complexes in which XY=an anionic O,O-chelated ligand compared to a neutral N,N-chelated ligand, and the mechanism more dissociative in character. The O,O-chelated XY=maltolato (mal) [M(eta(6)-p-cym)(mal)Cl] complexes, in which p-cvm=p-cymene, M=Os-II (1) and Run (2). were synthesised and the X-ray crystal structures of I and 2-2H(2)O determined. Their hydrolysis rates were rapid (too fast to follow by NMR spectroscopy). The aqua adduct of the Os-II complex 1 was 1.6 pK(a) units more acidic than that of the Ru-II complex 2. Dynamic NMR studies suggested that O,O-chelate ring opening occurs on a millisecond timescale in coordinating proton-donor solvents, and loss of chelated mal in aqueous solution led to the formation of the hydroxo-bridged dimers [(eta(6)-p-cyrn)M(mu-OH)(3)M(eta(6)-p-cym)](+). ne proportion of this dimer in solutions of the Os-II complex 1 increased with dilution and it predominated at micromolar concentrations, even in the presence of 0.1 M NaCl (conditions close to those used for cytotoxicity testing). Although 9-ethylguanine (9-EtG) binds rapidly to Os-II in 1 and more strongly (log K=4.4) than to Ru-II in 2 (log K=3.9), the Os-II adduct [Os(eta(6)-p-cym)(mal)-(9EtG)](+) was unstable with respect to formation of the hydroxo-bridged dimer at micromolar concentrations. Such insights into the aqueous solution chemistry of metal-arene complexes under biologically relevant conditions will aid the rational design of organometallic anticancer agents.
Item Type: | Journal Article | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||
Journal or Publication Title: | Chemistry : A European Journal | ||||
Publisher: | Wiley - V C H Verlag GmbH & Co. KGaA | ||||
ISSN: | 0947-6539 | ||||
Official Date: | 2007 | ||||
Dates: |
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Volume: | Volume 13 | ||||
Number: | Number 9 | ||||
Number of Pages: | 13 | ||||
Page Range: | pp. 2601-2613 | ||||
DOI: | 10.1002/chem.200601152 | ||||
Status: | Peer Reviewed | ||||
Publication Status: | Published | ||||
Access rights to Published version: | Restricted or Subscription Access |
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