應用密度泛函數理論計算於金屬錯合物催化反應：I. 以二茂鐵或含鈷之類三明治雙牙磷基配位之衍生鈀金屬錯合物催化Suzuki-Miyaura偶合反應II. 以含氮雜環碳烯-

Abstract

In topic part I, several dppf- and dppc-derived bidentate phosphines ligated palladium complexes catalyzed Suzuki-Miyaura reactions have been studied using density functional theory. Unexpectedly, the catalytic reactions employing ligands having two phosphine biting sites on the same cyclpentadienyl or cyclobutadiene ring, such as 1,2-dmpf or 1,2-dmpc, had been verified energetically more favorable than those on different rings. The application of a secondary phosphine oxide in coupling reaction is an unfavorable choice unless for the purpose of storage. Topic Part II Allylic Aminations Catalyzed by N-Heterocyclic Carbene-Pyridine Ligated Palladium Complexes Abstract The allylic aminations catalyzed by N-heterocyclic carbene-pyridine ligated palladium complexes have been studied by using density functional theory (B3LYP/LanL2DZ). All the geometries were fully optimized, and the potential energy surfaces for the allylic aminations have been discussed in detail. Comparison of the activation barriers and reaction enthalpies were used to determine the relative reactivities of the potential diastereomers of cationic palladium-allyl complexes. As a result, the theoretical investigation suggests that the nucleophilic addition on the syn-allyl fragment is a more favorable pathway for the allylic aminations. These calculations are consistent with the experimental results.