Reaction Control of Dynamic Complexes

有机过渡金属配合物的配位键具有金属-碳键、金属-杂原子键和金属-金属键的灵活性。这种柔性表现为在静态和动态的分子框架中，由施加到配合物上的小的物理和化学刺激引起的容易的键形成和断裂，以及分子参数如电子布居、键长和键角的变化。本项目旨在通过对有机过渡金属配合物的结构-反应性关系的系统研究，开发新的合成方法和功能材料。双核钌配合物催化烯丙醇异构化反应研究发现含氧官能团的苯系双核钌配合物催化烯丙醇异构化为相应的醛和酮。这种催化的关键特征提出依赖于两种底物的氧原子和苯配体的侧臂的容易的配位和解离。2. Me_3Al促进的η^2-酮与η^2-烯烃在镍催化下的偶联反应镍催化下羰基和烯烃环化生成氧杂环己基镍内酯被认为是镍催化偶联反应的关键步骤。在这项研究中，分离出了一种表征良好的镍（0）的η^2-羰基-η^2-烯烃配合物，并测定了其结构。用Me_3Al处理该配合物可促进羰基-烯烃的氧化环化反应，生成Ni与Al通过缺电子甲基桥配位的五元氧杂镍配合物

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