Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart (Germany).
Angew Chem Int Ed Engl. 2014 Feb 10;53(7):1790-4. doi: 10.1002/anie.201309767. Epub 2014 Jan 30.
During the past 10 years iron-catalyzed reactions have become established in the field of organic synthesis. For example, the complex anion Fe(CO)3 (NO) , which was originally described by Hogsed and Hieber, shows catalytic activity in various organic reactions. This anion is commonly regarded as being isoelectronic with Fe(CO)4 , which, however, shows poor catalytic activity. The spectroscopic and quantum chemical investigations presented herein reveal that the complex ferrate Fe(CO)3 (NO) cannot be regarded as a Fe(-II) species, but rather is predominantly a Fe(0) species, in which the metal is covalently bonded to NO(-) by two π-bonds. A metal-N σ-bond is not observed.
在过去的 10 年中，铁催化反应在有机合成领域已经确立。例如，最初由 Hogsed 和 Hieber 描述的[Fe(CO)3(NO)]-复杂阴离子在各种有机反应中表现出催化活性。这种阴离子通常被认为与[Fe(CO)4]2-等电子，然而后者表现出较差的催化活性。本文提出的光谱和量子化学研究表明，[Fe(CO)3(NO)]-配合物不能被视为 Fe(-II)物种，而是主要是 Fe(0)物种，其中金属通过两个π键与 NO-共价键合。没有观察到金属-N σ 键。
