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 0020-1669

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Abstract

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
ISSN:	0020-1669
Date:	5 April 2010
Volume:	Vol.49
Number:	No.7
Number of Pages:	10
Page Range:	pp. 3310-3319
Identification Number:	10.1021/ic902243q
Status:	Peer Reviewed
Publication Status:	Published
Access rights to Published version:	Restricted or Subscription Access
URI:	http://wrap.warwick.ac.uk/id/eprint/6159

Data sourced from Thomson Reuters' Web of Knowledge

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