Reductive Elimination Leading to C-C Bond Formation in Gold(III) Complexes: A Mechanistic and Computational Study

Luca Rocchigiani, Julio Fernandez-Cestau, Peter HM Budzelaar, Manfred Bochmann

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22 Citations (Scopus)
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Abstract

The factors affecting the rates of reductive C-C cross-coupling reactions in gold(III) aryls were studied using complexes that allow easy access to a series of electronically modified aryl ligands, as well as to gold methyl and vinyl complexes, using the pincer compounds (C^N^C)AuR (R = C6F5, CH=CMe2, Me and p-C6H4X, where X = OMe, F, H, But, Cl, CF3, or NO2) as starting materials (C^N^C = 2,6-(4′-ButC6H3)2pyridine dianion). Protodeauration followed by addition of 1 equiv. SMe2 leads to the quantitative generation of the thioether complexes [(C^N-CH)AuR(SMe2)]+. Upon addition of a second SMe2 pyridine is displaced, which triggers reductive aryl-R elimination. The rates for these cross-couplings increase in the sequence k(vinyl) > k(aryl) >> k(C6F5) > k(Me). Vinyl-aryl coupling is particularly fast, 1.15 × 10–3 L mol–1 s–1 at 221 K, while both C6F5 and Me couplings encountered higher barriers for the C-C bond forming step. Using P(p-tol)3 in place of SMe2 greatly accelerates C–C couplings. Computational modelling shows that in the C^N bonded compounds displacement of N by a donor L is required before the aryl ligands can adopt a conformation suitable for C-C bond formation, so that elimination takes place from a four-coordinate intermediate. C-C bond formation is rate limiting. In the non-chelating case, reductive C(sp2)-C(sp2) elimination from three-coordinate cations [(Ar1)(Ar2)AuL]+ is almost barrierless, particularly if L = phosphine.
Original languageEnglish
Pages (from-to)8893-8903
Number of pages11
JournalChemistry - A European Journal
Volume24
Issue number35
Early online date14 Apr 2018
DOIs
Publication statusPublished - 21 Jun 2018

Keywords

  • gold complex
  • reaction mechanisms
  • calculations
  • C-C bond formation
  • reductive elimination

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