Mechanism of Mercuration of Ferrocene: General Treatment of Electrophilic Substitution of Ferrocene Derivatives
作者:Allan F. Cunningham
DOI:10.1021/om960815+
日期:1997.3.1
ratio of C5H5:C5D5 attack ranges from 5.2−6.5, depending upon the mercurating agent employed. In contrast to the Friedel−Crafts acetylation of 1, mercuration does not give rise to intramolecular interannularproton transfers. Under certain conditions, a complex, 6, can be isolated that contains both carbon−mercury and iron−mercury bonds. Taking these facts into account, a mechanism for the mercuration of
(五茂铁环戊二烯基)环戊二烯基铁(II)1的汞基优先出现在C 5 H 5环上。C 5 H 5:C 5 D 5侵蚀的比例在5.2-6.5之间,这取决于所使用的汞化剂。与1的Friedel-Crafts乙酰化相反,汞不引起分子内环内质子转移。在某些条件下,一个复杂的,6可以被隔离,既包含碳汞键又包含铁汞键。考虑到这些事实,提出了一种二茂铁汞化的机理,其中,在决定形成碳汞键的速率之前,先将汞化剂与铁原子进行预络合,并伴随着H +的损失。结合我们先前有关二茂铁的乙酰化和质子交换的工作,这项研究基于亲电试剂的反应性和所得二茂铁产品的铁原子的碱性,可以制定二茂铁的亲电取代的一般机理。
TAKENAKA, HIDEYUKI;SATO, TOMOHIRO;NISHIZAWA, MUGIO, TETRAHEDRON LETT., 30,(1989) N7, C. 2267-2268