title: Monohydroxamic acids and bridging dihydroxamic acids as chelators to ruthenium(III) and as nitric oxide donors: syntheses, speciation studies and nitric oxide releasing investigations.
abstract: The synthesis and spectroscopic characterisation of novel mononuclear Ru(III)(edta)(hydroxamato) complexes of general formula [Ru(H2edta)(monoha)] (where monoha = 3- or 4-NH2, 2-, 3- or 4-C1 and 3-Me-phenylhydroxamato), as well as the first example of a Ru(III)-N-aryl aromatic hydroxamate, [Ru(H2edta)(N-Me-bha)].H2O (N-Me-bha = N-methylbenzohydroxamato) are reported. Three dinuclear Ru(III) complexes with bridging dihydroxamato ligands of general formula [{Ru(H2edta)}2(mu-diha)] where diha = 2,6-pyridinedihydroxamato and 1,3- or 1,4-benzodihydroxamato, the first of their kind with Ru(III), are also described. The speciation of all of these systems (with the exception of the Ru-1,4-benzodihydroxamic acid and Ru-N-methylbenzohydroxamic systems) in aqueous solution was investigated. We previously proposed that nitrosyl abstraction from hydroxamic acids by Ru(III) involves initial formation of Ru(III)-hydroxamates. Yet, until now, no data on the rate of nitric oxide (NO) release from hydroxamic acids has been published. We now describe a UV-VIS spectroscopic study, where we monitored the decrease in the ligand-to-metal charge-transfer band of a series of Ru(III)-monohydroxamates with time, with a view to gaining an insight into the NO-releasing properties of hydroxamic acids.
authors.affiliation: Centre for Synthesis & Chemical Biology, Department of Pharmaceutical & Medicinal Chemistry, Royal College of Surgeons in Ireland, 123 St. Stephens Green, Dublin 2, Ireland.
authors.forename: Darren
authors.initials: D
authors.lastname: Griffith
authors.forename: Krystyna
authors.initials: K
authors.lastname: Krot
authors.forename: Jedd
authors.initials: J
authors.lastname: Comiskey
authors.forename: Kevin B
authors.initials: KB
authors.lastname: Nolan
authors.forename: Celine J
authors.initials: CJ
authors.lastname: Marmion
mesh_terms: D001952:Bridged-Ring Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D006877:Hydroxamic Acids / Q000737:chemistry*; D015394:Molecular Structure; D009569:Nitric Oxide / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D012428:Ruthenium / Q000737:chemistry*; D013056:Spectrophotometry, Ultraviolet
chemical_list: D001952:Bridged-Ring Compounds; D006877:Hydroxamic Acids; D009942:Organometallic Compounds; D009569:Nitric Oxide; D012428:Ruthenium