Controlling the reactivity of ruthenium(II) arene complexes by tether ring-opening
Pizarro, Ana M., Melchart, Michael, Habtemariam, Abraha, Salassa, Luca, Fabbiani, Francesca P. A., Parsons, S. (Simon) and Sadler, P. J.. (2010) Controlling the reactivity of ruthenium(II) arene complexes by tether ring-opening. Inorganic Chemistry, Vol.49 (No.7). pp. 3310-3319. ISSN 0020-1669Full text not available from this repository.
Official URL: http://dx.doi.org/10.1021/ic902243q
The closed-and open-tethered Ru-II eta(6)-arene complexes [Ru-II(eta(6):eta(1)-C6H5(C6H4)NH2)(en)]Cl-2 (2) and [Ru-II(eta(6)-C6H5(C6H4)NH2)Cl(en)]Cl (3), where en is ethylenediamine, have been synthesized and their X-ray structures determined. Interconversion between 2 and 3, that is, tethered-arene ring-closure and ring-opening, in different solvents has been investigated. Complex 2 opens in dimethylsulfoxide (DMSO) by solvent-induced dissociation of the NH2 group of the pendant arm. In methanol, however, equilibrium between 2 and 3 is reached after 12 h when both species coexist in solution in a ratio of 2:1 (open/closed). In water (pH 7), complete ring closure of 3 to 2 at 298 K occurs in less than 2 h. The tether ring of complex 2 opens at basic pH and closes at neutral pH. Complex 2 opens over time (18 h) in concentrated HCl. The opening-closing process is fully reversible in the pH range 2-12. Density Functional Theory calculations have been used to obtain insights into the electronic structure of complexes 2 and 3, their UV vis properties, and their stability compared to their aqua derivatives. Control of tether-ring-opening can contribute toward a strategy for activation and for achieving cytotoxic selectivity of ruthenium arene anticancer drugs.
|Item Type:||Journal Article|
|Subjects:||Q Science > QD Chemistry|
|Divisions:||Faculty of Science > Chemistry|
|Library of Congress Subject Headings (LCSH):||Ruthenium compounds, Aromatic compounds, Transition metal complexes -- Therapeutic use, Organometallic compounds -- Therapeutic use, Antineoplastic agents|
|Journal or Publication Title:||Inorganic Chemistry|
|Publisher:||American Chemical Society|
|Official Date:||5 April 2010|
|Number of Pages:||10|
|Page Range:||pp. 3310-3319|
|Access rights to Published version:||Restricted or Subscription Access|
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