| Summary: | 碩士 === 國立中興大學 === 化學系所 === 103 === A new type of secondary phosphine oxides (SPOs, 3a-3c) containing N-P bond have been successfully prepared. These ligands are stable toward air and moisture, and thereby are good for long time storage. The molecular structures of 3b and palladium complexes 4a, 4b were determined by single crystal X-ray diffraction methods. After screening the ligands for Catellani reaction to synthesize 1-methyl-9H-carbazole, 3b exhibited satisfactory efficiency. Furthermore, a mechanism was proposed to accomdate the process for the formation of 1-substituted carbazoles by C-C and C-N bonds cross-coupling.
The catalytic performances of these ligands on Catellani type N-H activation reactions were studied. Unfortunately, the results are not as good as expected. However, we obtained the palladium complex 2A from the crystal growing process. Since the intermediate products 3A and 5A are available, we proposed a reaction machanisim which is correlated to the formation of 2A complex. Besides, we were able to repeat the N-H activation reaction which reported by Bach and obtained the crystal structure of intermediate 1A. In addition, a series of closely related compounds 1B, 2B and 3B were obtained from similar reactions by replacing norbornene to dicyclopentadiene. It is worthy of noting that theses crystal structures are unique for palladium complexes containing norbornene or dicyclopentadiene.
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