Synthesis and Structure of Tetradentate Nitrogen Ligands and Linear Tetranuclear Metal-Chain Complexes

• Main Authors: Lin, Tzu-Wei, 林子偉
• Other Authors: Peng, Shie-Ming
• Format: Others
• Language: zh-TW
• Published: 1998
• Online Access: http://ndltd.ncl.edu.tw/handle/21411715231419476385

碩士 === 國立臺灣大學 === 化學系研究所 === 86 === Linear multi-nuclear metal chain complexes are highly interested both in metal -metal bond theory and potential application as a molecular metalwire. Several linear tri- and penta-nuclear metal chain complexes have been synthesized suc h as nickel, cobalt, and chromium ...etc. In these "odd"-multi-nuclear metal c hain complexes, the metal chain is helically surrounded by four organic ligand s to perform a wire-like structure and there are axial ligands in the both ter minal of 6m. metal chain. The interaction between metals is affected by the ax ial ligands. The properties of complexes with different axial ligands have bee n studied. However there is no reports about synthesizing metal chain complexe s of "even"-multi-nuclear system, such as tetra- or hexa-nuclear metal chain c omplexes.The aim of this thesis is the synthesis of tetra-nuclear metal chain complexes. In the beginning, several tetradentate nitrogen bridged ligands wer e synthesized then the proper one was choosed. The tetranuclear metal chain Ni II complex [Ni4((4-ph-dpda)4] was synthesized successfully with the ligand N-p henyl-dipyridyldiamine named as H2ph-dpda. Various spectroscopic methods, in p articular mass spectrometry (FAB), and X-ray diffraction were applied to chara cterize this complex. The tetranuclear NiII chain is helically surrounded by f our ph-dpda anion ligands and there is no axial ligand in this complex. In [Ni4((4-ph-dpda)4] complex, the distances of Ni-Ni are equal to 2.30 A and of Ni-N are equal to 1.91 A which consist with the characterstic bond lengths of low spin NiII. This complex was proposed to be diamagnetic. It is noticeble that the tetranuclear NiII complex will convert to trinuclear NiII complex in the solution, which contains chloro-solvent.