Isolation and X-ray structures of four Rh(PCP) complexes including a Rh(I) dioxygen complex with a short O-O bond

Handle URI:
http://hdl.handle.net/10754/562846
Title:
Isolation and X-ray structures of four Rh(PCP) complexes including a Rh(I) dioxygen complex with a short O-O bond
Authors:
Hayashi, Yukiko; Szalda, David J.; Grills, David C.; Hanson, Jonathan C.; Huang, Kuo-Wei ( 0000-0003-1900-2658 ) ; Muckerman, James T.; Fujita, Etsuko
Abstract:
The 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.
KAUST Department:
KAUST Catalysis Center (KCC); Chemical Science Program; Physical Sciences and Engineering (PSE) Division; HCL
Publisher:
Elsevier BV
Journal:
Polyhedron
Issue Date:
Jul-2013
DOI:
10.1016/j.poly.2012.10.006
Type:
Article
ISSN:
02775387
Is Supplemented By:
Hayashi, 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; DOI:10.5517/ccyvqvb; HANDLE:http://hdl.handle.net/10754/624727; Hayashi, 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; DOI:10.5517/ccyvqt9; HANDLE:http://hdl.handle.net/10754/624726; Hayashi, 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; DOI:10.5517/ccyvqs8; HANDLE:http://hdl.handle.net/10754/624725; Hayashi, 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; DOI:10.5517/ccyvqr7; HANDLE:http://hdl.handle.net/10754/624724
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorHayashi, Yukikoen
dc.contributor.authorSzalda, David J.en
dc.contributor.authorGrills, David C.en
dc.contributor.authorHanson, Jonathan C.en
dc.contributor.authorHuang, Kuo-Weien
dc.contributor.authorMuckerman, James T.en
dc.contributor.authorFujita, Etsukoen
dc.date.accessioned2015-08-03T11:12:30Zen
dc.date.available2015-08-03T11:12:30Zen
dc.date.issued2013-07en
dc.identifier.issn02775387en
dc.identifier.doi10.1016/j.poly.2012.10.006en
dc.identifier.urihttp://hdl.handle.net/10754/562846en
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.en
dc.publisherElsevier BVen
dc.subjectPCPen
dc.subjectPinceren
dc.subjectRh-O2 complexen
dc.subjectRhodiumen
dc.titleIsolation and X-ray structures of four Rh(PCP) complexes including a Rh(I) dioxygen complex with a short O-O bonden
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentChemical Science Programen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentHCLen
dc.identifier.journalPolyhedronen
dc.contributor.institutionChemistry Department, Brookhaven National Laboratory, Upton, NY 11973-5000, United Statesen
dc.contributor.institutionElectronics Materials Division, Electronics Department, Nagase ChemteX Corporation, 236, Tatsunocho-nakai, Tatsuno, Hyogo 679-4124, Japanen
dc.contributor.institutionResearch Collaborator at Brookhaven National Laboratory, Department of Natural Sciences, Baruch College, NY 10010, United Statesen
kaust.authorHuang, Kuo-Weien
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/ccyvqvben
dc.relation.isSupplementedByDOI:10.5517/ccyvqvben
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624727en
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/ccyvqt9en
dc.relation.isSupplementedByDOI:10.5517/ccyvqt9en
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624726en
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/ccyvqs8en
dc.relation.isSupplementedByDOI:10.5517/ccyvqs8en
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624725en
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/ccyvqr7en
dc.relation.isSupplementedByDOI:10.5517/ccyvqr7en
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624724en
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