Reductive Elimination Reactions in Gold(III) Complexes Leading to C(sp<sup>3</sup>)–X (X = C, N, P, O, Halogen) Bond Formation: Inner-Sphere vs S<sub>N</sub>2 Pathways
作者:Alejandro Portugués、Miguel Ángel Martínez-Nortes、Delia Bautista、Pablo González-Herrero、Juan Gil-Rubio
DOI:10.1021/acs.inorgchem.2c04166
日期:2023.1.30
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
导致在 Au(III) 配合物的配位层中形成 C-杂原子键的反应并不常见,其机制尚不为人所知。这项工作报告了一系列含有不同 Au-杂原子键的 Au(III) 甲基配合物的合成和还原消除反应。配合物 [Au(CF 3 )(Me)(X)(PR 3 )] (R = Ph, X = OTf, OClO 3 , ONO 2 , OC(O)CF 3 , F, Cl, Br; R = Cy, X = Me, OTf, Br)是通过反式-[Au(CF 3 )(Me) 2 (PR 3 )] (R = Ph, Cy)与HX的反应得到的。阳离子络合物cis -[Au(CF 3 )(Me)(PPh3 ) 2 ]OTf由[Au(CF 3 )(Me)(OTf)(PPh 3 )]与PPh 3反应得到。加热这些复合物导致 MeX(X = Me、Ph 3 P +、OTf、OClO 3、ONO 2、OC(O)CF 3、F、C