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

器官金属络合物的配位键的特征是金属碳，金属hetero原子和金属金属键的灵活性。灵活性由易于键合的形成和裂解，以及分子参数的变化，例如电子总体，键长和键角，在静态和动态分子框架中，由小的物理和化学刺激引起的静态和动态分子框架。该项目的目的是通过系统的投资来开发新的合成方法论和功能材料，通过系统的投资在器官金属络合物中的结构反应关系。烯丙基醇的促成酸酸催化的双核氟噻酮络合物催化含有苯配体的苯二苯甲酸含量由氧官能组固定为氧官能组，从而催化了与Allyllache and allyllys and a allyllys and a allylys and and anderlys and and anderlys and allylylys and a allyllys and a allylys and a allylys and a allylys and ket kete and kete se se。 Key features of this catalysis are proposed Specifically, the isomerization might have been proceeding 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 Oxanickel-lasycle被认为是某些镍催化的耦合反应的关键步骤。在这项研究中，分离了镍（0）的特征良好的η^2-Carbonyl-η^2-烷烃复合物并确定其结构。用ME_3AL处理这种复合物的羰基 - 烷基促进了氧化环化，从

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)