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

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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