Isolation and X-ray structures of four Rh(PCP) complexes including a Rh(I) dioxygen complex with a short O-O bond
Type
ArticleAuthors
Hayashi, YukikoSzalda, David J.
Grills, David C.
Hanson, Jonathan C.
Huang, Kuo-Wei

Muckerman, James T.
Fujita, Etsuko
KAUST Department
Chemical Science ProgramHomogeneous Catalysis Laboratory (HCL)
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Date
2013-07Permanent link to this record
http://hdl.handle.net/10754/562846
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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.Citation
Hayashi, Y., Szalda, D. J., Grills, D. C., Hanson, J. C., Huang, K.-W., Muckerman, J. T., & Fujita, E. (2013). Isolation and X-ray structures of four Rh(PCP) complexes including a Rh(I) dioxygen complex with a short O–O bond. Polyhedron, 58, 106–114. doi:10.1016/j.poly.2012.10.006Publisher
Elsevier BVJournal
PolyhedronRelations
Is Supplemented By:- [Dataset]
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: 10754/624727 - [Dataset]
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: 10754/624726 - [Dataset]
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: 10754/624725 - [Dataset]
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: 10754/624724
ae974a485f413a2113503eed53cd6c53
10.1016/j.poly.2012.10.006