Room-temperature cyclometallation of amines, imines and oxazolines with [MCl<sub>2</sub>Cp*]<sub>2</sub>(M = Rh, Ir) and [RuCl<sub>2</sub>(p-cymene)]<sub>2</sub>
作者:David L. Davies、Omar Al-Duaij、John Fawcett、Marco Giardiello、Stephen T. Hilton、David R. Russell
DOI:10.1039/b303737a
日期:——
N,N-Dimethylbenzylamine, alkyl and aryl imines derived from benzaldehyde, and 2-phenyl-4,4-dimethyloxazoline all undergo cyclometallation with [IrCl2Cp*]2
(Cp*
=
η-C5Me5) when treated with NaOAc in dichloromethane at room temperature. The imines are also cyclometallated by [RhCl2Cp*]2 under the same conditions whilst only N-alkyl imines are cyclometallated by [RuCl2(p-cymene)]2. The role of acetate in the cyclometallation is more than just as a base. X-Ray structures of cyclometallated complexes [MClC6H4-2-C(H)NCH2CH2OMe-κC,N}(η-ring)](M = Ir, Rh ring = Cp*; M = Ru, ring =
p-cymene), [MClC6H4-2-C(H)NCH2CH2OMe-κC,N}Cp*](M = Ir, Rh), [RuCl(η2-O2CMe)(p-cymene)] and [IrCl2(NH2Ph)Cp*] are reported.
室温下,在二氯甲烷中用 NaOAc 处理 N,N-二甲基苄胺、苯甲醛衍生的烷基和芳基亚胺以及 2-苯基-4,4-二甲基噁唑啉时,它们都会与 [IrCl2Cp*]2 (Cp* = η-C5Me5)发生环金属化反应。在相同条件下,[RhCl2Cp*]2 也能使亚胺环金属化,而只有 N-烷基亚胺能被 [RuCl2(p-cymene)]2环金属化。醋酸盐在环金属化反应中的作用不仅仅是作为碱。环金属化配合物 [MClC6H4-2-C(H)NCH2CH2OMe-κC,N}(η-环)](M = Ir,Rh 环 = Cp*)的 X 射线结构;报告了[MClC6H4-2-C(H)NCH2CH2OMe-κC,N}Cp*](M = Ir、Rh)、[RuCl(η2-O2CMe)(p-cymene)]和[IrCl2(NH2Ph)Cp*]。