Study On The Synthesis And Their Reactions Of Cyclopalladated Ferrocenylpyrimidine Complexes

In this thesis, the synthesis, characterization and crystal structures of a series of 4-chloro-2-pyrimidinylferrocene,5-bromo-2-pyridinylferrocene,1,1'-bisferrocenylpyr-imidine and their monophosphine-palladacycle and biscyclopalladated complexes were reported. We explore their role and catalytic activity in C-C and C-N bond forming reaetions via Suzuki reaetion and Buchwald-Hartwig amination.1. A series of new containing N-donor ferrocenyl ligand 1-3 was conveniently prepared via palladium-catalyzed coupling reaction, their cyclopalladated complexes 4-10 also obtained from the cyclopalladation reactions and bridge-splitting reactions (Scheme 1). These compounds have been characterized by NMR, IR, ESI-MS and elemental analysis. Additionally, part of their detailed structures has been determined by X-ray single-crystal diffraction. The complex 9 was found to be a disubstituted monocyclopalladated complex, while the complex 10 was a disubstituted biscyclopa-lladated complex. 2. The synthesis of metalloligands bearing cyclopalladated ferrocenyl unit via Suzuki reactions and Buchwald-Hartwig aminations. we explore the effect of 4,6,8 in C-C and C-N bond forming reaetions (Scheme 2). These results indicated that 4,6 were not only act as substrates but also as catalysts in suzuki reactions because of they were palladacycle containing halide. The corresponding metalloligand was readily obtained from 4 and amines in the absence of base due to the strong activity of chloride atom(in pyrimidine ring), even the strong organic base was used, the coupling of analogous palladacycle containing halide 6 and amines was also unsuccessful, the complex 8 was active in the Buchwald-Hartwig aminations.