Design of Coordinatively Unsaturated Iron Species for Homogeneous Catalysis

通过选择合适的配位体，设计了三种配位不饱和铁，并研究了它们对烯烃和相关不饱和化合物的反应性。三氮杂环壬烷（TACN）衍生物是铁（II）配合物的良好配体。配位不饱和16e-(TACN) FeX2是原子转移自由基聚合的催化剂。提出了两种16e-Fe（II）菌种的生成概念；一种是基于氮取代基的空间体积控制的卤素桥接二聚体和催化活性单体之间的良好平衡，另一种是弱配位体对活性单体的稳定。含两个甲酰基的14 -有机铁配合物和一个含缺电子烯的四乙二胺配体处理导致了甲酰基配体的偶联反应以及甲酰基与α，β-不饱和酮的共轭加成。氮桥式二聚体前驱体与烯烃反应生成环有机硅化合物。

Three types of coordinatively unsaturated iron species were designed by appropriate choice of auxialiry ligands, and their reactivity towards alkenes and related unsaturated compounds was investigated. Triazacyclononane(TACN) derivatives were a good ligand for Fe(II) complexes. Coordinatively unsaturated 16e-(TACN) FeX2 species behaved as a catalyst for atom transfer radical polymerization. Two concepts for generation of 16e-Fe(II) species were proposed ; one was based on favorable equiliblim between a halogen-bridged dimer and a catalytically active monomer controlled by steric bulkiness of nitrogen substituents of TACN, whereas another was stabilization of active monomeric species by weakly coordinating ligands. Treatment of a 14e-organoiron complex bearing two mesityl groups and a tetraethylenediamine ligand with electron deficient alkenes resulted in coupling reaction of the mesityl ligands as well as conjugate addition of a mesityl group toα,β-unsaturated ketones. Disilametallacylic 16e-Fe(II) species was generated from a nitrogen-bridged dimer precursor reacted with alkenes to form cyclic organosilicon compounds.