Kinetics and Mechanisms of the Reactions of Diaryl- and Dialkylgermylenes with Alcohols and Ethers in Solution
作者:William J. Leigh,*、Farahnaz Lollmahomed、Cameron R. Harrington、Jacklyn M. McDonald
DOI:10.1021/om060595s
日期:2006.10.1
The reactions of methanol, tert-butanol, and THF with a series of simple germylene derivativesdimethyl- (GeMe2), diphenyl- (GePh2), and dimesitylgermylene (GeMes2; Mes = 2,4,6-trimethylphenyl)have been studied in hexane solution at 25 °C by laser flash photolysis methods. The results are consistent with rapid, reversible reaction to form weakly stabilized Lewis acid−base complexes, which exhibit UV
甲醇,叔丁醇和THF与一系列简单的亚二甲基衍生物二甲基-(GeMe 2),二苯基-(GePh 2)和二聚三苯甲基亚甲基(GeMes 2; Mes = 2,4,6-三甲基苯基)的反应已经进行。在25°C的己烷溶液中通过激光闪光光解方法进行了研究。结果与快速,可逆反应形成弱稳定的路易斯酸碱配合物一致,路易斯酸碱配合物在290-360 nm范围内表现出最大的UV吸收,并随着混合阶动力学的衰减而伴随着相应的Digermene Ge 2 R 4的形成( R = Me,Ph或Mes)。可以测量GePh 2形成配合物的绝对速率常数对于所有三种底物,GeMe 2均具有四氢呋喃,发现在(4-10)×10 9 M -1 s -1范围内变化。在所有情况下均测量平衡常数。对于GeMes 2,它们的变化范围为1.2到15 M -1,以MeOH> t-BuOH> THF的顺序降低,而GeMe 2和GePh 2的则为2-4个数量级,并且以THF>