期刊
INORGANIC CHEMISTRY
卷 -, 期 -, 页码 -出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.2c04166
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This study reports on the synthesis and reductive elimination reactions of Au(III) methyl complexes. The reactions leading to the formation of C-heteroatom bonds in Au(III) complexes are uncommon and their mechanisms are not well known. The obtained results show that nucleophilic substitution should be considered as a likely reductive elimination pathway in Au(III) alkyl complexes.
The reactions leading to the formation of C-heteroatom bonds in the coordination sphere of Au(III) complexes are uncommon, and their mechanisms are not well known. This work reports on the synthesis and reductive elimination reactions of a series of Au(III) methyl complexes containing different OClO3, ONO2, OC(O)CF3, F, Cl, Br; R = Cy, X = Me, OTf, Br) were obtained by the reaction of trans-[Au(CF3)(Me)(2)(PR3)] (R = Ph, Cy) with HX. The cationic complex cis-[Au(CF3)(Me)(PPh3)(2)]OTf was obtained by the reaction of [Au(CF3)(Me)(OTf)(PPh3)] with PPh3. Heating these complexes led to the reductive elimination of MeX (X = Me, Ph3P+, OTf, OClO3, ONO2, OC(O)CF3, F, Cl, Br). Mechanistic studies indicate that these reductive elimination reactions occur either through (a) the formation of tricoordinate intermediates by phosphine dissociation, followed by reductive elimination of MeX, or (b) the attack of weakly coordinating anionic (TfO- or ClO4-) or neutral nucleophiles (PPh3 or NEt3) to the Au-bound methyl carbon. The obtained results show for the first time that the nucleophilic substitution should be considered as a likely reductive elimination pathway in Au(III) alkyl complexes.
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