A Straightforward Electrochemical Approach to Imine‐ and Amine‐bisphenolate Metal Complexes with Facile Control Over Metal Oxidation State
A Straightforward Electrochemical Approach to Imine‐ and Amine‐bisphenolate Metal Complexes with Facile Control Over Metal Oxidation State
复制标题
一种简单的电化学方法，可轻松控制金属氧化态，制备亚胺和胺双酚金属配合物
作者：
Michael R. Chapman;Susan E. Henkelis;N. Kapur;B. Nguyen;C. Willans
制备有机金属和配位化合物如席夫碱配合物的合成方法多种多样，选择的路线取决于许多因素，如金属-配体组合和金属氧化态。在这项工作中，我们已经表明，电化学方法可以用来合成各种金属salen/salan络合物，其中包括不同的金属配体组合和氧化态。广泛的应用已被证明通过在温和和环境条件下制备的34个配合物。 通过简单地改变反应条件，对金属氧化态（MII/III/IV，其中M=Fe，Mn）进行了前所未有的控制。沿着这条路线，一个通用的协议开关进行了描述，允许访问分析纯的FeII/III-salen复合物。调节电化学电位，选择性金属化的Mn/Ni合金，专门提供MnII/IV-salen配合物的高产率。
Abstract Synthetic methods to prepare organometallic and coordination compounds such as Schiff‐base complexes are diverse, with the route chosen being dependent upon many factors such as metal–ligand combination and metal oxidation state. In this work we have shown that electrochemical methodology can be employed to synthesize a variety of metal–salen/salan complexes which comprise diverse metal–ligand combinations and oxidation states. Broad application has been demonstrated through the preparation of 34 complexes under mild and ambient conditions. Unprecedented control over metal oxidation state (MII/III/IV where M=Fe, Mn) is presented by simple modification of reaction conditions. Along this route, a general protocol‐switch is described which allows access to analytically pure FeII/III–salen complexes. Tuning electrochemical potential, selective metalation of a Mn/Ni alloy is also presented which exclusively delivers MnII/IV–salen complexes in high yield.