Ruthenium(II) arene complexes containing four- and five-membered monoanionic O,O-chelate rings

Michael Melchart; Abraha Habtemariam; Simon Parsons; Stephen A. Moggach; Peter J. Sadler

doi:10.1016/j.ica.2005.12.059

Ruthenium(II) arene complexes containing four- and five-membered monoanionic O,O-chelate rings

Michael Melchart, Abraha Habtemariam, Simon Parsons, Stephen A. Moggach, Peter J. Sadler

School of Molecular Sciences

Research output: Contribution to journal › Article › peer-review

43 Citations (Scopus)

Abstract

Optimization of the design of half-sandwich organometallic Ru^II arene complexes as anticancer agents depends on control of ligand exchange reactions. We have studied the aqueous chemistry of complexes containing O,O-chelate rings. The presence of the four-membered O,O-chelate ring from acetate (AcO) in [η⁶-p-cymene)Ru(AcO)Cl] was confirmed by X-ray crystallography, but in solution the acetate ligand was labile and the hydroxo-bridged dimer [((η⁶-p-cymene)Ru)₂(μ-OH)₃]⁺ readily formed. The dimer was relatively unreactive towards 9-ethyl guanine. The tropolonato (trop) complex [(η⁶-p-cymene)Ru(trop)Cl] was stable in aqueous media and the X-ray crystal structure of the aqua adduct [(η⁶-p-cymene)Ru(trop)(H₂O)]CF₃SO₃, containing a five-membered O,O-chelate ring from trop, was determined. [(η⁶-p-cymene)Ru(trop)Cl] reacted with guanosine to form N7 adducts and with adenosine to form both N7 and N1 adducts. Competitive reactions with guanosine and adenosine gave rise to guanosine:adenosine adducts in a ca. 1.3:1 mol ratio.

Original language	English
Pages (from-to)	3020-3028
Number of pages	9
Journal	Inorganica Chimica Acta
Volume	359
Issue number	9
DOIs	https://doi.org/10.1016/j.ica.2005.12.059
Publication status	Published - 1 Jun 2006

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title = "Ruthenium(II) arene complexes containing four- and five-membered monoanionic O,O-chelate rings",

abstract = "Optimization of the design of half-sandwich organometallic RuII arene complexes as anticancer agents depends on control of ligand exchange reactions. We have studied the aqueous chemistry of complexes containing O,O-chelate rings. The presence of the four-membered O,O-chelate ring from acetate (AcO) in [η6-p-cymene)Ru(AcO)Cl] was confirmed by X-ray crystallography, but in solution the acetate ligand was labile and the hydroxo-bridged dimer [((η6-p-cymene)Ru)2(μ-OH)3]+ readily formed. The dimer was relatively unreactive towards 9-ethyl guanine. The tropolonato (trop) complex [(η6-p-cymene)Ru(trop)Cl] was stable in aqueous media and the X-ray crystal structure of the aqua adduct [(η6-p-cymene)Ru(trop)(H2O)]CF3SO3, containing a five-membered O,O-chelate ring from trop, was determined. [(η6-p-cymene)Ru(trop)Cl] reacted with guanosine to form N7 adducts and with adenosine to form both N7 and N1 adducts. Competitive reactions with guanosine and adenosine gave rise to guanosine:adenosine adducts in a ca. 1.3:1 mol ratio.",

keywords = "Adenine, Guanine, Hydrolysis, Organometallic, Ruthenium half-sandwich, Tropolone",

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AU - Melchart, Michael

AU - Habtemariam, Abraha

AU - Parsons, Simon

AU - Moggach, Stephen A.

AU - Sadler, Peter J.

PY - 2006/6/1

Y1 - 2006/6/1

N2 - Optimization of the design of half-sandwich organometallic RuII arene complexes as anticancer agents depends on control of ligand exchange reactions. We have studied the aqueous chemistry of complexes containing O,O-chelate rings. The presence of the four-membered O,O-chelate ring from acetate (AcO) in [η6-p-cymene)Ru(AcO)Cl] was confirmed by X-ray crystallography, but in solution the acetate ligand was labile and the hydroxo-bridged dimer [((η6-p-cymene)Ru)2(μ-OH)3]+ readily formed. The dimer was relatively unreactive towards 9-ethyl guanine. The tropolonato (trop) complex [(η6-p-cymene)Ru(trop)Cl] was stable in aqueous media and the X-ray crystal structure of the aqua adduct [(η6-p-cymene)Ru(trop)(H2O)]CF3SO3, containing a five-membered O,O-chelate ring from trop, was determined. [(η6-p-cymene)Ru(trop)Cl] reacted with guanosine to form N7 adducts and with adenosine to form both N7 and N1 adducts. Competitive reactions with guanosine and adenosine gave rise to guanosine:adenosine adducts in a ca. 1.3:1 mol ratio.

AB - Optimization of the design of half-sandwich organometallic RuII arene complexes as anticancer agents depends on control of ligand exchange reactions. We have studied the aqueous chemistry of complexes containing O,O-chelate rings. The presence of the four-membered O,O-chelate ring from acetate (AcO) in [η6-p-cymene)Ru(AcO)Cl] was confirmed by X-ray crystallography, but in solution the acetate ligand was labile and the hydroxo-bridged dimer [((η6-p-cymene)Ru)2(μ-OH)3]+ readily formed. The dimer was relatively unreactive towards 9-ethyl guanine. The tropolonato (trop) complex [(η6-p-cymene)Ru(trop)Cl] was stable in aqueous media and the X-ray crystal structure of the aqua adduct [(η6-p-cymene)Ru(trop)(H2O)]CF3SO3, containing a five-membered O,O-chelate ring from trop, was determined. [(η6-p-cymene)Ru(trop)Cl] reacted with guanosine to form N7 adducts and with adenosine to form both N7 and N1 adducts. Competitive reactions with guanosine and adenosine gave rise to guanosine:adenosine adducts in a ca. 1.3:1 mol ratio.

KW - Adenine

KW - Guanine

KW - Hydrolysis

KW - Organometallic

KW - Ruthenium half-sandwich

KW - Tropolone

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ER -

Ruthenium(II) arene complexes containing four- and five-membered monoanionic O,O-chelate rings

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