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

本课题利用现代电子结构理论对具有柔性电子结构的过渡金属配合物进行了理论研究。利用密度泛函理论和后Hartree-Fock方法对σ键与镍(0)配合物的氧化加成进行了理论研究。密度泛函理论没有定量地呈现反应的正确特征，当采用高质量基组时，高度复杂的后 Hartree-Fock 方法呈现出正确的结果。为了对实际配合物进行后 Hartree-Fock 计算，我们新提出了位移算子，我们可以结合大取代基的电子效应，这种位移算子实际上非常有效，我们成功地用这个位移算子再现了大型金属配合物的电子结构。因为多核过渡金属配合物是理论化学的挑战性研究课题。，我们从理论上研究了几种双核和三核配合物的电子结构和键合性质，例如，铼双核配合物要求我们使用多参考电子结构理论。金属-金属键，其键序比形式值小得多。光致自旋捕获复合物是一种有趣的材料，最近，因为它们在分子器件中的潜在能力，我们从理论上研究了光致自旋捕获特征。铁（III）络合物的不同之处在于，中间自旋态的势能面与低自旋态和高自旋态的势能面相当接近，这一新结果引起了实验领域的广泛关注。过渡金属配合物的催化反应非常在理论化学中很有趣，因为这种催化剂通常是有用且复杂的。在这里，我们的理论研究清楚地表明活性物质是铱（V）络合物，并且催化反应是通过铱发生的。 (III)和铱(V)种类较少。

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。