title: Selective lability of ruthenium(II) arene amino acid complexes.
abstract: A series of organometallic complexes of the form [(PhH)Ru(amino acid)](+) have been synthesized using amino acids able to act as tridentate ligands. The straightforward syntheses gave enantiomerically pure complexes with two stereogenic centers due to the enantiopurity of the chelating ligands. Complexes were characterized in the solid-state and/or solution-state where the stability of the complex allowed. The propensity toward labilization of the coordinatively saturated complexes was investigated. The links between complex stability and structural features are very subtle. Nonetheless, H/D exchange rates of coordinated amino groups reveal more significant differences in reactivity linked to metallocycle ring size resulting in decreasing stability of the metallocycle as the amino acid side-chain length increases. The behavior of these systems in acid is unusual, apparently labilizing the carboxylate residue of the amino acid. This acid-catalyzed hemilability in an organometallic is relevant to the use of Ru(II) arenes in medicinal contexts due to the relatively low pH of cancerous cells.
authors: University of Cambridge, Chemistry Department, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
authors: Tom G
authors: TG
authors: Scrase
authors: University of Cambridge, Chemistry Department, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
authors: Michael J
authors: MJ
authors: O'Neill
authors: University of Cambridge, Chemistry Department, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
authors: Andrew J
authors: AJ
authors: Peel
authors: University of Cambridge, Chemistry Department, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
authors: Paul W
authors: PW
authors: Senior
authors: University of Cambridge, Chemistry Department, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
authors: Peter D
authors: PD
authors: Matthews
authors: University of Cambridge, Chemistry Department, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
authors: Heyao
authors: H
authors: Shi
authors: University of Cambridge, Chemistry Department, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
authors: Sally R
authors: SR
authors: Boss
authors: University of Cambridge, Chemistry Department, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
authors: Paul D
authors: PD
authors: Barker
mesh_terms: D000596:Amino Acids / Q000737:chemistry*; D001554:Benzene / Q000737:chemistry; D008024:Ligands; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000596:Amino Acids; D008024:Ligands; D009942:Organometallic Compounds; D012428:Ruthenium; D001554:Benzene