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Reaction Control of Dynamic Complexes

动态配合物的反应控制

基本信息

批准号：
14078218
负责人：
KUROSAWA Hideo
金额：
$ 15.62万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research on Priority Areas
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2005
项目状态：
已结题

项目摘要

Coordination bonds of organotransition metal complexes are characterized by the flexibility of metal-carbon, metal-hetero atom, and metal-metal bonds. The flexibility is represented by facile bond formation and cleavage, as well as change of molecular parameters such as electron population, bond length and bond angle, in both static and dynamic molecular frameworks caused by a small physical and chemical stimuli applied to the complexes. This project aims at development of new synthetic methodology and functional materials through a systematic investigation of the structure-reactivity relation in organotransition metal complexes.Llsomerization of allyl alcohol catalyzed by dinuclear ruthenium complexesDinuclear ruthenium complexes containing benzene ligand tethered by oxygen functional group were found to catalyze isomerization of allyl alcohols to the corresponding aldehydes and ketones. Key features of this catalysis are proposed to rely on facile coordination and dissociation of oxygen atoms of both substrates and the side arm of the benzene ligand. Specifically, the isomerization might have proceeded via coordination of allyloxo ligand, followed by β-H elimination and H shift to the terminal carbon of α, β-enone intermediate.2.Coupling of η^2-ketone and η^2-alkene on nickel promoted by Me_3AlCyclization of carbonyl group and alkene group on nickel forming an oxanickelacycle has been postulated to be a key step in some nickel catalyzed coupling reactions. In this study a well-characterized η^2-carbonyl-η^2-alkene complex of nickel(0) was isolated and its structure determined. Treatment of this complex with Me_3Al promoted oxidative cyclization of carbonyl-alkene groups to give 5-membered oxanickelacycle with Ni coordinated by electron-deficient methyl bridge with AL

有机过渡金属配合物的配位键具有金属-碳、金属-杂原子、金属-金属键的柔性。灵活性表现为在静态和动态分子框架中，由于施加到配合物的小的物理和化学刺激而导致容易的键形成和断裂，以及分子参数（例如电子数量、键长和键角）的变化。本项目旨在通过系统研究有机过渡金属配合物的结构-反应性关系，开发新的合成方法和功能材料。双核钌配合物催化烯丙醇的异构化发现含有氧官能团束缚的苯配体的双核钌配合物可以催化烯丙醇异构化为相应的化合物。醛和酮。提出这种催化的关键特征依赖于两种底物和苯配体侧臂的氧原子的轻松配位和解离。具体来说，异构化可能是通过烯丙氧基配体的配位进行的，然后是β-H消除和H转移到α, β-烯酮中间体的末端碳。2.Me_3Al促进的镍上的η^2-酮和η^2-烯烃的偶联形成氧杂镍环的镍上的羰基和烯基的环化被认为是一些镍催化偶联反应的关键步骤。在本研究中，分离出一种具有良好表征的镍(0) η^2-羰基-η^2-烯烃络合物并确定了其结构。用 Me_3Al 处理该配合物促进了羰基烯烃基团的氧化环化，得到 5 元氧杂镍环，其中 Ni 通过缺电子甲基桥与 AL 配位

项目成果

期刊论文数量（32）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Sensuke Ogoshi, Masaki Morita, Hideo Kurosawa: "Synthesis, Structure and Reactivity of η^3-1-Hydroxyallyl Complex : Protonation of α,β-Unsaturated Carbonyl Compound Bound to Palladium(O) and Platinum (O)"J.Am.Chem.Soc.. 125. 9020-9021 (2003)

Sensuke Ogoshi、Masaki Morita、Hideo Kurosawa：“η^3-1-Hydroxyallyl Complex 的合成、结构和反应性：与钯 (O) 和铂 (O) 结合的 α,β-不饱和羰基化合物的质子化”J.Am.化学学会. 125. 9020-9021 (2003)