@article {ISI:000270186500047,
	title = {Influence of oxygenation on the reactivity of ruthenium-thiolato bonds in arene anticancer complexes: insights from XAS and DFT.},
	journal = {J. Am. Chem. Soc.},
	volume = {131},
	number = {37},
	year = {2009},
	month = {sep},
	pages = {13355{\textendash}61},
	publisher = {American Chemical Society},
	abstract = {Thiolate ligand oxygenation is believed to activate cytotoxic half-sandwich [(eta(6)-arene)Ru(en)(SR)](+) complexes toward DNA binding. We have made detailed comparisons of the nature of the Ru-S bond in the parent thiolato complexes and mono- (sulfenato) and bis- (sulfinato) oxygenated species including the influence of substituents on the sulfur and arene. Sulfur K-edge XAS indicates that S(3p) donation into the Ru(4d) manifold depends strongly on the oxidation state of the sulfur atom, whereas Ru K-edge data suggest little change at the metal center. DFT results are in agreement with the experimental data and allow a more detailed analysis of the electronic contributions to the Ru-S bond. Overall, the total ligand charge donation to the metal center remains essentially unchanged upon ligand oxygenation, but the origin of the donation differs markedly. In sulfenato complexes, the terminal oxo group makes a large contribution to charge donation and even small electronic changes in the thiolato complexes are amplified upon ligand oxygenation, an observation which carries direct implications for the biological activity of this family of complexes. Details of Ru-S bonding in the mono-oxygenated complexes suggest that these should be most susceptible to ligand exchange, yet only if protonation of the terminal oxo group can occur. The potential consequences of these results for biological activation are discussed.},
	keywords = {Antineoplastic Agents, Antineoplastic Agents: chemical synthesis, Antineoplastic Agents: chemistry, Antineoplastic Agents: metabolism, AROMATIC, Aromatic: chemistry, DFT, DNA, DNA: metabolism, Drug Design, ELECTRONS, HYDROCARBONS, LIGANDS, metal-based drugs, models, MOLECULAR, Molecular Conformation, ORGANOMETALLIC COMPOUNDS, Organometallic Compounds: chemical synthesis, Organometallic Compounds: chemistry, Organometallic Compounds: metabolism, OXYGEN, Oxygen: chemistry, quantum theory, ruthenium, Ruthenium: chemistry, Spectrum Analysis, Sulfhydryl Compounds, Sulfhydryl Compounds: chemistry, X-Rays, XAS},
	issn = {1520-5126},
	doi = {10.1021/ja903405z},
	url = {http://www.ncbi.nlm.nih.gov/pubmed/19719101 http://dx.doi.org/10.1021/ja903405z},
	author = {Sriskandakumar, Thamayanthy and Petzold, Holm and Bruijnincx, Pieter C A and Habtemariam, Abraha and Sadler, Peter J and Kennepohl, Pierre}
}
@article {ISI:000251974000023,
	title = {An electronic rationale for observed initiation rates in ruthenium-mediated olefin metathesis: charge donation in phosphine and N-heterocyclic carbene ligands.},
	journal = {J. Am. Chem. Soc.},
	volume = {129},
	number = {51},
	year = {2007},
	month = {dec},
	pages = {15774{\textendash}6},
	chapter = {15774},
	abstract = {Ru K-edge XAS data indicate that second generation ruthenium-based olefin metathesis precatalysts (L = N-heterocyclic carbene) possess a more electron-deficient metal center than in the corresponding first generation species (L = tricyclohexylphosphine). This surprising effect is also observed from DFT calculations and provides a simple rationale for the slow phosphine dissociation kinetics previously noted for second-generation metathesis precatalysts.},
	keywords = {ALKENES, Alkenes: chemistry, BOND, carbenes, CATALYSTS, CL, DFT, ELECTRONS, Heterocyclic Compounds, Heterocyclic Compounds: chemistry, HYDROCARBONS, Hydrocarbons: chemistry, KINETICS, LIGANDS, MECHANISM, METHANE, Methane: analogs \& derivatives, Methane: chemistry, MOIETY, NHC LIGANDS, OLEFIN METATHESIS, phosphines, Phosphines: chemistry, RAY-ABSORPTION SPECTROSCOPY, ruthenium, Ruthenium: chemistry, TRANSITION-METAL-COMPLEXES, XAS},
	isbn = {0002-7863},
	issn = {1520-5126},
	doi = {10.1021/ja0747674},
	url = {<Go to ISI>://000251974000023 http://www.ncbi.nlm.nih.gov/pubmed/18047332},
	author = {Getty, Kendra and Delgado-Jaime, Mario Ulises and Kennepohl, Pierre}
}
