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. 2014 Feb 14;50(13):1533-6.
doi: 10.1039/c3cc48914k.

Rationale for the sluggish oxidative addition of aryl halides to Au(I)

Madeleine Livendahl  1 , Charles Goehry, Feliu Maseras, Antonio M Echavarren
Affiliations

Rationale for the sluggish oxidative addition of aryl halides to Au(I)

Madeleine Livendahl et al. Chem Commun (Camb). .

Abstract

The oxidative addition of Csp(2)-Br or Csp(2)-I bonds to gold(I) does not take place even under very favorable intramolecular conditions that could form five- or six-membered gold(III) metallacycles. DFT calculations reveal that although this process could be feasible thermodynamically, it is kinetically very sluggish.

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Figures

Scheme 1
Scheme 1. Hypothetical intramolecular oxidative addition of Csp2–X bonds to Au(i) to form Au(iii) metallacycles II.
Fig. 1
Fig. 1. ORTEP plot (50% thermal ellipsoids) of the crystal structure of complex 2a (a) and 2b (b).
Fig. 2
Fig. 2. ORTEP plot (50% thermal ellipsoids) of the crystal structure of complexes 4a (a) and 5 (b).
Fig. 3
Fig. 3. M06 optimized structure of transition states 2t1ts and 1tts colour codes: red = Br, purple = P, yellow = Au, green = Cl.
See this image and copyright information in PMC

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