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Volumn 29, Issue 17, 2010, Pages 3683-3685

Unexpected Ccarbene-X (X: I, Br, Cl) reductive elimination from N-heterocyclic carbene copper halide complexes under oxidative conditions

Author keywords

[No Author keywords available]

Indexed keywords

CARBENES; CATALYST DESIGNS; COPPER HALIDE; DECOMPOSITION PATHWAY; DENSITY-FUNCTIONAL CALCULATIONS; HALIDE COMPLEXES; LATE TRANSITION METALS; LONE PAIR ELECTRONS; N-HETEROCYCLIC CARBENES; NHC LIGANDS; OXIDATIVE CONDITIONS; REACTION MECHANISM; REDUCTIVE ELIMINATION; SIMPLIFIED MODELS;

EID: 77956409611     PISSN: 02767333     EISSN: 15206041     Source Type: Journal    
DOI: 10.1021/om1005726     Document Type: Article
Times cited : (34)

References (57)
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    • note
    • 2, respectively.
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    • note
    • 1H NMR signals similar to that of a reported NHC-ligated Cu(II) dimer, (20b) suggesting that C-F formation is slower than the comproportionation between Cu(I) and Cu(III).
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    • Cl by cyclic voltammetry at low temperatures (ca. -40 °C).
    • Cl by cyclic voltammetry at low temperatures (ca. -40 °C).
  • 47
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    • All calculations were performed at the level of B3LYP/6-311+G* by the Gaussian 03 program. The solvation effect was estimated by the PCM/UA0 model. Relative free energies are used in the computational discussion. See Supporting Information for more detailed descriptions of the computational methods.; et al., Revision E.01; Gaussian, Inc.: Wallingford, CT.
    • All calculations were performed at the level of B3LYP/6-311+G* by the Gaussian 03 program. The solvation effect was estimated by the PCM/UA0 model. Relative free energies are used in the computational discussion. See Supporting Information for more detailed descriptions of the computational methods. Frisch, M. J.; et al. Gaussian03, Revision E.01; Gaussian, Inc.: Wallingford, CT, 2004.
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    • Frisch, M.J.1
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    • 3CN) according to the method in
    • 3CN) according to the method in: Wertz, D. H. J. Am. Chem. Soc. 1980, 102, 5316-5322
    • (1980) J. Am. Chem. Soc. , vol.102 , pp. 5316-5322
    • Wertz, D.H.1
  • 49
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    • -1 activation free energy was calculated for this step (fluorine transfer) at a lower-level method (B3LYP/6-311+G//B3LYP/ LANL2DZ). (19)
    • -1 activation free energy was calculated for this step (fluorine transfer) at a lower-level method (B3LYP/6-311+G//B3LYP/ LANL2DZ). (19)
  • 50
    • 77956416627 scopus 로고    scopus 로고
    • 6 is proposed as an intermediate in the reaction. It might ligate to copper in the final uncharacterized Cu(II) product. Coordination of MeCN to 3 might facilitate the oxidation. However, the corresponding three-coordinate species could not be located computationally.
    • 6 is proposed as an intermediate in the reaction. It might ligate to copper in the final uncharacterized Cu(II) product. Coordination of MeCN to 3 might facilitate the oxidation. However, the corresponding three-coordinate species could not be located computationally.
  • 51
    • 34548591384 scopus 로고    scopus 로고
    • I species. Zhang, S.-L.; Liu, L.; Fu, Y.; Guo, Q.-X. Organometallics 2007, 26, 4546-4554 By contrast, no analogous intermediate was located computationally for our system.
    • (2007) Organometallics , vol.26 , pp. 4546-4554
    • Zhang, S.-L.1    Liu, L.2    Fu, Y.3    Guo, Q.-X.4
  • 52
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    • These include two isomers of 7, one five-coordinate Cu(III) species, and a complex with 6 coordinated to 5. (19)
    • These include two isomers of 7, one five-coordinate Cu(III) species, and a complex with 6 coordinated to 5. (19)
  • 53
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    • See Supporting Information.
    • See Supporting Information.
  • 56
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    • 2 (1.30 V vs NHE) (9) seems possible.
    • 2 (1.30 V vs NHE) (9) seems possible.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.