Reductive elimination leading to C-C bond formation in gold(III) complexes: A mechanistic and computational study

Rocchigiani, Luca, Fernandez-Cestau, Julio, Budzelaar, Peter H. M. and Bochmann, Manfred ORCID: https://orcid.org/0000-0001-7736-5428 (2018) Reductive elimination leading to C-C bond formation in gold(III) complexes: A mechanistic and computational study. Chemistry - A European Journal, 24 (35). pp. 8893-8903. ISSN 0947-6539

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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.

Item Type:	Article
Uncontrolled Keywords:	gold complex,reaction mechanisms,calculations,c-c bond formation,reductive elimination
Faculty \ School:	Faculty of Science > School of Chemistry
UEA Research Groups:	Faculty of Science > Research Groups > Chemistry of Light and Energy Faculty of Science > Research Groups > Chemistry of Materials and Catalysis
Depositing User:	Pure Connector
Date Deposited:	16 Apr 2018 11:33
Last Modified:	20 Apr 2023 23:44
URI:	https://ueaeprints.uea.ac.uk/id/eprint/66771
DOI:	10.1002/chem.201801277

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