Theoretical Study of Flexible Molecular Systems Possessing Complexed Electronic Structure tOWARDS Reaction Design and Control

具有复杂电子结构的柔性分子体系的理论研究及其反应设计与控制

基本信息

批准号：
18350005
负责人：
SAKAKI Shigeyoshi
金额：
$ 9.65万
依托单位：
Kyoto University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2006
资助国家：
日本
起止时间：
2006 至 2007
项目状态：
已结题

项目摘要

Theoretical studies of transition metal complexes bearing flexible electronic structure were carried out with modern electronic structure theories in this project.Oxidative addition of σ-bond to nickel(0) complex was theoretically investigated with density functional theory and post-Hartree-Fock method. Though the density functional theory did not present quantitatively correct features of the reaction, highly sophisticated post-Hartree-Fock method presented correct results when high quality basis sets were employed.To perform post-Hartree-Fock calculation of real complexes, we newly proposed shift operator with which we can incorporate electronic effects of bulky substituent. This shift operator is very effective ; actually, we succeeded to reproduce the electronic structure of large metal complexes with this shift operator.Because multinuclear transition metal complexes are challenging research subjects of theoretical chemistry, we theoretically investigated electronic structure and … More bonding nature of several dinuclear and trinuclear complexes. For instance, rhenium dinuclear complexes requested us to use multi-reference electronic structure theory. Those rhenium dinuclear complexes have metal-metal bond, bond order of which is much smaller than the formal value.Light-induced spin-trapping complex is one of interesting materials, recently, because of their potential abilities for molecular devices. We theoretically investigated light-induced spin trapping feature of iron(III) complex. Interestingly, the potential energy surface of the intermediate spin state is rather close to those of the low spin and high spin states, against the general understanding. This new result attracts a lot of interests from the experimental field.Catalytic reaction by transition metal complexes is very interesting in theoretical chemistry, because such catalyses are useful and complicated in general. Here, iridium-catalyzed direct silylation of benzene was theoretically investigated. Our theoretical study clearly shows that active species is iridium(V) complex and the catalytic reaction takes place through iridium(III) and iridium(V) species. Less

在该项目中，使用现代电子结构理论进行了具有柔性电子结构的过渡金属复合物的理论研究。理论上用密度功能理论和hartree后折原方法对镍键添加到镍（0）复合物进行了氧化添加。尽管密度功能理论没有提出反应的定量正确特征，但是当采用高质量的基础集时，高度复杂的哈特里后盘方法却提出了正确的结果。要对真实复合物的近距离计算进行实际复合物的计算，我们新提出的转移操作员可以使用，我们可以将其纳入大型亚titutuntuent的电子效应。这个转变操作员非常有效。实际上，我们成功地使用了此移位操作员重现了大金属配合物的电子结构。由于多核过渡金属复合物是理论化学的挑战研究主题，因此我们在理论上研究了电子结构，并且……几种核和三核复合物的更具键合性。例如，rhenuium dinuclear综合体要求我们使用多参考电子结构理论。那些rhenuium dinuclear络合物具有金属金属键，其键顺序比正式值小得多。光希望诱导的自旋陷阱复合物是最近的有趣材料之一，因为它们对分子设备的潜在能力。我们理论上研究了铁（III）复合物的光诱导的自旋诱捕特征。有趣的是，中间自旋状态的势能表面与一般理解相对接近低自旋和高旋转状态的势能表面。这一新结果吸引了实验领域的许多兴趣。在理论化学中，过渡金属复合物的催化反应非常有趣，因为这种催化剂通常是有用且复杂的。在这里，理论上研究了虹膜催化的直接苯乙烯。我们的理论研究清楚地表明，活性物种是虹膜（V）复合物，催化反应通过虹膜（III）和虹膜（V）物种进行。较少的

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）

Phosphorous-containing hybrid calixphyrins : Promising mixed-donor ligands for visible and efficient palladium catalysts

含磷杂化杯盏蛋白：用于可见且高效的钯催化剂的有前途的混合供体配体

DOI：
发表时间：
2006
期刊：
J. Am. Chem. Soc 128
影响因子：
0
作者：
Y.;Matano;T.;Miyajima;T.;Nakabuchi;H.;Imahori;N.;Ochi;S.;Sakaki
通讯作者：
Sakaki

Theoretical Study of Low-Spin, High-Spin, and Intermediate-Spin States of [Fe-III(pap)(2)]+ (pap = N-2-pyridylmethylidene-2-hydroxyphenylaminato). Mechanism of Light-Induced Excited Spin State Trapping

[Fe-III(pap)(2)]（pap = N-2-吡啶基亚甲基-2-羟基苯氨基）低自旋、高自旋和中自旋态的理论研究。

DOI：
发表时间：
2007
期刊：
Journal of Physical Chem. A 111
影响因子：
0
作者：
H. Ando;Y. Nakao;H. Sato;S. Sakaki
通讯作者：
S. Sakaki

New Analysis of Molecular orbital wave functions based on resonance theory

基于共振理论的分子轨道波函数新分析

DOI：
发表时间：
2006
期刊：
J.Phys.Chem.A 108
影响因子：
0
作者：
Atsushi Ikeda;Yoshihide Nakao;Shigeyoshi Sakaki
通讯作者：
Shigeyoshi Sakaki

Deep Blue Mixed-Valenct PtIII-PtIII-PtII Complex [Pt3Br2 (?-pz)6] (pz = pyrazolate) Showing Valence-Detrapping Behavior in Solution

深蓝色混合价 PtIII-PtIII-PtII 络合物 [Pt3Br2 (?-pz)6]（pz = 吡唑盐）在溶液中显示价态脱陷行为

DOI：
发表时间：
2006
期刊：
Chem. Eur. J. 12
影响因子：
0
作者：
Keisuke Umakoshi;Takashi Kojima;Yung Hun Kim;Masayoshi Ohnishi;Yoshihide Nakao;Shigeyoshi Sakaki
通讯作者：
Shigeyoshi Sakaki

Thoretical study of low-spin, high-spin,andintermediate-spin states of [Fe-III8pap)(2)](+) (pap=N-2-pyridylmethylidene-2-hydroxyphenylaminato). Mechanism of light-induced wxcited spin state trapping

[Fe-III8pap)(2)]( ) (pap=N-2-吡啶基亚甲基-2-羟基苯氨基)低自旋、高自旋和中自旋态的理论研究。