@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 {Kennepohl2009, title = {X-ray spectroscopic approaches to the investigation and characterization of photochemical processes.}, journal = {J. Syncr. Rad.}, volume = {16}, number = {Pt 4}, year = {2009}, pages = {484{\textendash}8}, publisher = {International Union of Crystallography}, abstract = {Despite a wealth of studies exemplifying the utility of the 2-5 keV X-ray range in speciation and electronic structure elucidation, the exploitation of this energy regime for the study of photochemical processes has not been forthcoming. Herein, a new endstation set-up for in situ photochemical soft X-ray spectroscopy in the 2-5 keV energy region at the Stanford Synchrotron Radiation Lightsource is described for continuous photolysis under anaerobic conditions at both cryogenic and ambient temperatures. Representative examples of this approach are used to demonstrate the potential information content in several fields of study, including organometallic chemistry, biochemistry and materials chemistry.}, keywords = {Absorptiometry, METHIONINE, Methionine: analogs \& derivatives, Methionine: radiation effects, ORGANOMETALLIC COMPOUNDS, Organometallic Compounds: chemistry, Organometallic Compounds: radiation effects, Photochemical Processes, Photon, Photon: methods, Synchrotrons}, issn = {1600-5775}, doi = {10.1107/S0909049509021384}, url = {http://www.pubmedcentral.nih.gov/articlerender.fcgi?artid=2698811\&tool=pmcentrez\&rendertype=abstract}, author = {Kennepohl, Pierre and Wasinger, Erik C and DeBeer George, Serena} } @article {ISI:000254173600010, title = {N-heterocyclic carbene complexes of Rh: reaction with dioxygen without oxidation.}, journal = {J. Am. Chem. Soc.}, volume = {130}, number = {12}, year = {2008}, month = {mar}, pages = {3724{\textendash}5}, abstract = {The reaction of oxygen with rhodium complexes containing N-heterocyclic carbenes was found to give dioxygen complexes with rare square planar geometries and unusually short O-O bond lengths. Analysis of the bonding in these complexes by Rh L-edge X-ray absorption spectroscopy (XAS), Raman spectroscopy, and DFT calculations provides evidence for a bonding model in which singlet oxygen is bound to a Rh(I) d8 metal complex, rather than the more common Rh(III) d6 peroxo species with octahedral geometry and O-O bond lengths in the 1.4-1.5 A range.}, keywords = {chemical, DFT, dioxygen complexes, Heterocyclic Compounds, Heterocyclic Compounds: chemistry, METHANE, Methane: analogs \& derivatives, Methane: chemistry, models, MOLECULAR, molecular structure, ORGANOMETALLIC COMPOUNDS, Organometallic Compounds: chemical synthesis, Organometallic Compounds: chemistry, OXYGEN, Oxygen: chemistry, rhodium, Rhodium: chemistry, SPECTROMETRY, X-Ray Emission, X-Ray Emission: methods, XAS}, issn = {1520-5126}, doi = {10.1021/ja7108213}, url = {http://www.ncbi.nlm.nih.gov/pubmed/18321109}, author = {Praetorius, Jeremy M and Allen, Daryl P and Wang, Ruiyao and Webb, Jonathan D and Grein, Friedrich and Kennepohl, Pierre and Crudden, Cathleen M} } @article {3691, title = {The use of high-performance liquid chromatography for the speciation of organotin compounds}, journal = {Applied Organometallic Chemistry}, volume = {10}, number = {5}, year = {1996}, note = {ISI Document Delivery No.: UW081Times Cited: 24Cited Reference Count: 89}, month = {Jun}, pages = {339-362}, type = {Review}, abstract = {This review of the use of high-performance liquid chromatography (HPLC) for the speciation of organotin compounds which are primarily of significance in the marine environment, is divided into sections on the basis of the different HPLC modes of separation. However, it should be noted that such a classification does not exist in reality. For instance, in an ion-pair reversed-phase system the separation mechanism for the ionic solutes may be ion-pair partitioning, or ion exchange, or both. The relevant practical information (e.g. column type, mobile phase, method of detection and detection limit) is presented in tabular form. MET A brief overview of the reported detection MIP methods is included, because the delay in development of an easily interfaced, specific and sensitive detector has hindered the use of HPLC for organotin speciation studies. The literature reviewed covers publications from 1977, the year of the first application of HPLC to organotin speciation, to April 1995.}, keywords = {antifouling paints, ATOMIC-ABSORPTION SPECTROMETRY, BUTYLTIN COMPOUNDS, DIALKYLTIN HOMOLOGS, ELEMENTAL SPECIATION, environmental pollution, ENVIRONMENTAL-SAMPLES, FLUID CHROMATOGRAPHY, high-performance liquid chromatography, HPLC, marine environment, ORGANOMETALLIC COMPOUNDS, organotin, PHOTOMETRIC DETECTION, PLASMA-MASS-SPECTROMETRY, review, SIZE-EXCLUSION CHROMATOGRAPHY, SPECIATION, SUPERCRITICAL, tributyltin}, isbn = {0268-2605}, url = {://A1996UW08100002}, author = {Harrington, C. F. and Eigendorf, G. K. and Cullen, W. R.} } @article {7019, title = {NATURE OF THE CATALYTICALLY INACTIVE COBALT HYDRIDE FORMED UPON HYDROGENATION OF AROMATIC SUBSTRATES - STRUCTURE AND CHARACTERIZATION OF THE BINUCLEAR COBALT HYDRIDE [(PRI2P(CH2)3PPRI2)CO]2(H)(MU-H)3}, journal = {Inorganic Chemistry}, volume = {30}, number = {10}, year = {1991}, note = {ISI Document Delivery No.: FM296Times Cited: 6Cited Reference Count: 28}, month = {May}, pages = {2437-2441}, type = {Note}, keywords = {COMPLEXES, CRYSTAL, MOLECULAR-STRUCTURE, ORGANOMETALLIC COMPOUNDS, RADICAL-ANION, rhodium, STATE}, isbn = {0020-1669}, url = {://A1991FM29600039}, author = {Fryzuk,Michael D. and Ng, J. B. and Rettig, S. J. and Huffman, J. C. and Jonas, K.} } @article {7037, title = {A THIOLATE-BRIDGED DIRUTHENIUM DISODIUM COMPLEX}, journal = {Journal of the Chemical Society-Chemical Communications}, number = {11}, year = {1991}, note = {ISI Document Delivery No.: FQ589Times Cited: 9Cited Reference Count: 11}, month = {Jun}, pages = {773-774}, type = {Article}, abstract = {The tetranuclear complex [(CO)4(PPh3)2Ru2(mu-2-SEt)4(mu-3-SEt)2Na2(thf)2] (thf = tetrahydrofuran) has been synthesized; the two ruthenium centres are linked by a network consisting of four doubly- and two triply-bridging thiolate ligands and two sodium atoms.}, keywords = {ALKOXIDES, CHEMISTRY, CRYSTAL, LIGANDS, ORGANOMETALLIC COMPOUNDS, RUTHENIUM CLUSTERS}, isbn = {0022-4936}, url = {://A1991FQ58900018}, author = {Jessop, P. G. and Rettig, S. J. and James, Brian R.} }