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dc.contributor.authorHayashi, Yukiko
dc.contributor.authorSzalda, David J.
dc.contributor.authorGrills, David C.
dc.contributor.authorHanson, Jonathan C.
dc.contributor.authorHuang, Kuo-Wei
dc.contributor.authorMuckerman, James T.
dc.contributor.authorFujita, Etsuko
dc.date.accessioned2015-08-03T11:12:30Z
dc.date.available2015-08-03T11:12:30Z
dc.date.issued2013-07
dc.identifier.issn02775387
dc.identifier.doi10.1016/j.poly.2012.10.006
dc.identifier.urihttp://hdl.handle.net/10754/562846
dc.description.abstractThe reaction of RhCl3·H2O with tBu2P(CH2)5PtBu 2 afforded several complexes including [RhIII(H)Cl{ tBu2- P(CH2)2CH(CH2) 2PtBu2}] (1), [RhIIIHCl 2{tBu2P(CH2)5P tBu2}]2 (2), [RhICl{ tBu2P(CH2)2CH=CHCH2P tBu2}] (3) and [RhICl{tBu 2PCH2C(O)CH=CHCH2PtBu2}] (4). X-ray crystal structures of 3 and 4 showed that the C=C bond on the C 5 unit of tBu2P(CH2) 5PtBu2 is bound to Rh(I) in a η2 configuration. In 4, the Rh atom has a trigonal pyramidal coordination geometry. The X-ray crystal structure of 2 consists of two rhodium( III) centers bridged by two tBu2P(CH2)5P tBu2 ligands with two phosphorus atoms, one from each ligand, trans to one another. The crystal structure of the rhodium oxygen adduct with 1,3-bis(di-t-butylphosphinomethyl) benzene [RhO2{ tBu2PCH2(C6H3)CH 2PtBu2}] (5) was also investigated. In this species the O2 is η2 coordinated to the Rh(I) center with asymmetric Rh-O bond lengths (2.087(7) and 1.998(8) Å). The O-O bond distance is short (1.337(11) Å) with νO-O of 990.5 cm -1. DFT calculations on complex 5 yielded two η2- O2 structures that differed in energy by only 0.76 kcal/mol. The lower energy one (5a) had near C2 symmetry, and had nearly equal Rh-O bond lengths, while the higher energy structure (5b) had near Cs symmetry and generally good agreement with the experimental structure. The calculated UV-Vis and IR spectra of complex 5 are in excellent agreement with experiment. © 2012 Elsevier Ltd. All rights reserved.
dc.publisherElsevier BV
dc.subjectPCP
dc.subjectPincer
dc.subjectRh-O2 complex
dc.subjectRhodium
dc.titleIsolation and X-ray structures of four Rh(PCP) complexes including a Rh(I) dioxygen complex with a short O-O bond
dc.typeArticle
dc.contributor.departmentChemical Science Program
dc.contributor.departmentHomogeneous Catalysis Laboratory (HCL)
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Division
dc.identifier.journalPolyhedron
dc.contributor.institutionChemistry Department, Brookhaven National Laboratory, Upton, NY 11973-5000, United States
dc.contributor.institutionElectronics Materials Division, Electronics Department, Nagase ChemteX Corporation, 236, Tatsunocho-nakai, Tatsuno, Hyogo 679-4124, Japan
dc.contributor.institutionResearch Collaborator at Brookhaven National Laboratory, Department of Natural Sciences, Baruch College, NY 10010, United States
kaust.personHuang, Kuo-Wei
dc.relation.isSupplementedByHayashi, Y., Szalda, D. J., Grills, D. C., Hanson, J. C., Huang, K.-W., Muckerman, J. T., & Fujita, E. (2013). CCDC 889633: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccyvqvb
dc.relation.isSupplementedByDOI:10.5517/ccyvqvb
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624727
dc.relation.isSupplementedByHayashi, Y., Szalda, D. J., Grills, D. C., Hanson, J. C., Huang, K.-W., Muckerman, J. T., & Fujita, E. (2013). CCDC 889632: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccyvqt9
dc.relation.isSupplementedByDOI:10.5517/ccyvqt9
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624726
dc.relation.isSupplementedByHayashi, Y., Szalda, D. J., Grills, D. C., Hanson, J. C., Huang, K.-W., Muckerman, J. T., & Fujita, E. (2013). CCDC 889631: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccyvqs8
dc.relation.isSupplementedByDOI:10.5517/ccyvqs8
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624725
dc.relation.isSupplementedByHayashi, Y., Szalda, D. J., Grills, D. C., Hanson, J. C., Huang, K.-W., Muckerman, J. T., & Fujita, E. (2013). CCDC 889630: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccyvqr7
dc.relation.isSupplementedByDOI:10.5517/ccyvqr7
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624724


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