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Volumn 48, Issue 14, 2009, Pages 2510-2513

Elementary steps of gold catalysis: NMR spectroscopy reveals the highly cationic character of a "gold carbenoid"

Author keywords

Carbenes; Carbocations; Gold; Homogeneous catalysis; Reactive intermediates

Indexed keywords

CARBENES; CARBENOIDS; CARBOCATIONS; CYCLOPROPENES; ELEMENTARY STEPS; GOLD CATALYSIS; GOLD-CARBENES; HOMOGENEOUS CATALYSIS; NMR SPECTROSCOPY; REACTIVE INTERMEDIATE; REACTIVE INTERMEDIATES; RING OPENING;

EID: 70349778993     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200806059     Document Type: Article
Times cited : (227)

References (86)
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    • 2)] might be more adequately viewed as an iminium cation in the coordination sphere of a gold template, cf. Ref. [4] and literature therein.
    • 2)] might be more adequately viewed as an iminium cation in the coordination sphere of a gold template, cf. Ref. [4] and literature therein.
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    • For the full data set, see the Supporting Information
    • For the full data set, see the Supporting Information.
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    • In addition, the more basic phosphines do not undergo ligand exchange on the NMR timescale, as is the case for the PPh3 containing species 5. In some NMR samples of 5, there were no couplings between 31P and the protons or 13C atoms of the organometallic residue. This fact is attributed to a rapid exchange of ligated and free PPh3 in this complex. This exchange could be suppressed by carefully adjusting the stoichiometry of the reactants
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    • the metathesis activity of the gold carbene [(IMes)Au=CHPh]′ generated in the mass spectrometer is also worth considering. Strikingly, however, this species effects metathesis only for 1,2-dimethoxyethene, which delivers a Fischer carbene wherein the positive charge is well stabilized by the methoxy substituent; in contrast, regular olefins were found to undergo cyclopropanation, cf. Ref. [9b].
    • c) the metathesis activity of the gold carbene [(IMes)Au=CHPh]′ generated in the mass spectrometer is also worth considering. Strikingly, however, this species effects metathesis only for 1,2-dimethoxyethene, which delivers a Fischer carbene wherein the positive charge is well stabilized by the methoxy substituent; in contrast, regular olefins were found to undergo cyclopropanation, cf. Ref. [9b].


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.