Synthesis and Characterization of the Redox-active Carbodicarbene Gold Complexes and Bidentate BINAP-based Chiral Carbone-derivative with their Metal Complexes

• Main Authors: Shang-Ting Tsai, 蔡尚廷
• Other Authors: 王朝諺
• Format: Others
• Language: zh-TW
• Published: 2019
• Online Access: http://ndltd.ncl.edu.tw/handle/8btc27

碩士 === 國立中央大學 === 化學學系 === 107 === 　　Ligand design is an important part of organometallic chemistry and catalysis. The electronic parameters and steric hindrance of the ligand influence the reactivity of the metal complexes. The carbodicarbene (CDC), also known as ‘‘bent allene’’, is a new class of low-valent carbon specy. Its electron-donating ability is very strong due to its possession of two free electron pairs, which even surpasses the carbenes. It has emerged as a potential effective ligand next to the carbenes and phosphines. 　　In the first project, we have successfully isolated CDC-supported tricationic Au-complexes. The complexes are fully characterized by NMR and X-ray diffraction. These Au complexes are EPR-active that CDC moiety are shown to carried radical cations 　　In second project, we have successfully developed the chiral bidentate carbophosphinocarbene, which is based on the large steric hindrance chiral ligand ‘‘BINAP’’. In this work, we have an interesting in the electron-donating ability of the carbon center at the carbone-derivative, so we have done the experiment with palladium(II), gold(I), and copper(I) metal complexes. The single crystal X-ray structural analysis and NMR spectroscopic studies have been used to understand the coordination sphere. This carbone-derivative can play a bidentate ligand in palladium(II) complexes, but just be a monodentate ligand in gold(I) complexes. Interestingly, it can be not only monodentate ligand but also bidentate ligand in copper(I) complexes, which is dependent on the coordination ability of the counter-anion.