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dc.contributor.authorWilson, Justin Jeff
dc.contributor.authorFedoce Lopes, Juliana
dc.contributor.authorLippard, Stephen J.
dc.date.accessioned2011-07-07T19:02:54Z
dc.date.available2011-07-07T19:02:54Z
dc.date.issued2010-03
dc.identifier.issn0020-1669
dc.identifier.issn1520-510X
dc.identifier.urihttp://hdl.handle.net/1721.1/64766
dc.description.abstractThree new ligands of the general formula [RNHCH(py)2] (py = pyridine; R = tosyl, Ts-dpm; R = dansyl, Ds-dpm; R = 7-nitro-1,2,3-benzoxadiazole, NBD-dpm) have been synthesized and characterized. Reactions of these ligands with cis-[Pt(DMSO)2Cl2] (DMSO = dimethyl sulfoxide) in methanol affords [Pt(Ts-dpm)Cl2] (1), [Pt(Ds-dpm)Cl2] (2), and [Pt(NBD-dpm)Cl2] (3). The crystal structures of these complexes reveal bidentate coordination of the ligands to the Pt center with nonplanar chelate rings. Because of inequivalent substituents on the methine carbon atom of the ligands, distinct exo and endo isomers exist in the three complexes. X-ray analyses indicate that 1 crystallizes in the endo conformation, 2 in the exo conformation, and 3 as a mixture of the two conformers. The 1H NMR and 195Pt NMR spectra of the complexes display two sets of independent signals corresponding to the chemically inequivalent exo and endo conformers. The exo conformer was determined by 2D NMR spectroscopy to be thermodynamically favored for all three complexes. Density functional theory (DFT), time-dependent DFT, and atoms in molecules calculations were carried out for both conformers of 3 to investigate differences in their electronic structures and to explore intramolecular interactions. In the presence of dioxygen, 1 thermally decomposes at 60 °C to form several unidentified products. Compound 2 is thermally stable even in the presence of dioxygen and water but upon light exposure decomposes to form a new platinum(II) species with a 195Pt NMR shift of −2177 ppm. Compound 3 reacts both thermally and photochemically in the presence of dioxygen and trace amounts of water to form both 4-amino-7-nitro-2,1,3-benzoxadiazole and [Pt(dpk)Cl2] (dpk = di-2-pyridyl ketone). Oxidation of 1 and 3 with H2O2 in acetic acid affords a mixture of compounds, two of which contain dpm ligands bound in a tridentate manner to platinum.en_US
dc.description.sponsorshipNational Cancer Institute (U.S.) (CA034992)en_US
dc.description.sponsorshipBrazil. Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (Post-doctoral Fellowship (process 4470-08-7))en_US
dc.language.isoen_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.isversionofhttp://dx.doi.org/10.1021/ic100411pen_US
dc.rightsArticle is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.en_US
dc.sourceProf. Lippard via Erja Kajosaloen_US
dc.titleSynthesis, Characterization, and Photophysical Properties of Three Pt(II) Complexes Bearing Fluorescent Analogues of the Di-(2-pyridyl)methane Liganden_US
dc.typeArticleen_US
dc.identifier.citationWilson, Justin J., Juliana Fedoce Lopes, and Stephen J. Lippard. “Synthesis, Characterization, and Photophysical Properties of Three Platinum(II) Complexes Bearing Fluorescent Analogues of the Di-2-pyridylmethane Ligand.” Inorganic Chemistry 49.11 (2010) : 5303-5315.en_US
dc.contributor.departmentMassachusetts Institute of Technology. Department of Chemistryen_US
dc.contributor.approverLippard, Stephen J.
dc.contributor.mitauthorWilson, Justin Jeff
dc.contributor.mitauthorFedoce Lopes, Juliana
dc.contributor.mitauthorLippard, Stephen J.
dc.relation.journalInorganic Chemistryen_US
dc.eprint.versionAuthor's final manuscripten_US
dc.type.urihttp://purl.org/eprint/type/JournalArticleen_US
eprint.statushttp://purl.org/eprint/status/PeerRevieweden_US
dspace.orderedauthorsWilson, Justin J.; Fedoce Lopes, Juliana; Lippard, Stephen J.en
dc.identifier.orcidhttps://orcid.org/0000-0002-2693-4982
mit.licensePUBLISHER_POLICYen_US
mit.metadata.statusComplete


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