权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

Design of Coordinatively Unsaturated Iron Species for Homogeneous Catalysis

均相催化配位不饱和铁物种的设计

基本信息

批准号：
22655029
负责人：
NAGASHIMA Hideo
金额：
$ 2.21万
依托单位：
Kyushu University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Challenging Exploratory Research
财政年份：
2010
资助国家：
日本
起止时间：
2010 至 2011
项目状态：
已结题

项目摘要

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.

通过选择合适的配位配体，设计了三种配位不饱和铁物种，并考察了它们对烯烃及相关不饱和化合物的反应活性。三氮杂环烷(TACN)衍生物是Fe(II)络合物的良好配体。配位不饱和16E-(TACN)FeX2物种是原子转移自由基聚合的催化剂。提出了生成16E-Fe(II)物种的两个概念：一种是基于卤素桥联二聚体和催化活性单体之间的良好平衡，该平衡由TACN的氮取代基团的空间体积控制；另一种是通过弱配位配体稳定活性单体物种。含有两个甲苯基的14E-有机铁配合物和一个四乙二胺配体与缺电子烯烃反应，导致甲苯基的偶联反应和甲苯基与α，β-不饱和酮的共轭加成反应。氮桥联的二聚体前体与烯烃反应生成环状有机硅化合物，生成了双硅丙烯酰基16E-Fe(II)物种。

项目成果

期刊论文数量（0）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

トリアザシクロノナン配位子を有する単核鉄錯体の合成と原子移動型ラジカル重合反応活性の相関

三氮杂环壬烷配体单核铁配合物的合成及原子转移自由基聚合反应活性的相关性

DOI：
发表时间：
2012
期刊：
影响因子：
0
作者：
M. Nishiura;J. Baldamus;T. Shima;K. Mori;Z. Hou;中西崇一朗・砂田祐輔・河村充展・甲斐英知・笹本茜・小池展行・早川均・金仁華・永島英夫
通讯作者：
中西崇一朗・砂田祐輔・河村充展・甲斐英知・笹本茜・小池展行・早川均・金仁華・永島英夫

Hydrosilane reduction of tertiary carboxamides by iron carbonyl catalysts.