主族(S,Se,Te)三鐵羰基化合物與過渡金屬(Cu)及含氮、磷有機試劑的反應探討

• Main Authors: Yu-Xin Huang, 黃宇薪
• Other Authors: Minghuey Shieh
• Format: Others
• Language: zh-TW
• Published: 2008
• Online Access: http://ndltd.ncl.edu.tw/handle/90156389545085364818

碩士 === 國立臺灣師範大學 === 化學系 === 96 === [1] [EFe3(CO)9]2− (E = S, Se, Te)─Cu─dppm system When [Et4N]2[EFe3(CO)9] (E = S, Se, Te) was treated with [Cu(MeCN)4][BF4] and dppm (dppm = bis(diphenylphosphino)methane) in various ratios, a series of copper-incorporated polynuclear complexes, [{EFe3(C0)9}Cu2(dppm)(THF)] (E = S, 1a; Se, 1b; Te, 1c), [{EFe3(CO)9}Cu2(dppm)(MeCN)] (E = S, 2a; Se, 2b; Te, 2c), [{EFe3(CO)9}Cu2(dppm)] (E = S, 3a; Se, 3b; Te, 3c) and [{EFe3(CO)8}Cu2(dppm)2] (E=S, 4a; Se, 4c; Te, 4b), were obtained. Complex 3 can transform to 1 or 2 with THF or MeCN. Conversely, complex 1 and 2 can reconvert back to complex 3 upon removeal of solvent. Complexes 1 and 2 can further react with dppm to form 4, which was supported by DFT calculations. [2] [EFe3(CO)9]2− (E = S, Se, Te)─Cu─dppe system When [Et4N]2[EFe3(CO)9] (E = S, Se, Te) was treated with [Cu(MeCN)4][BF4] and dppe (dppe = 1,2-bis(diphenylphosphino)ethane) in various ratios, a series of copper-incorporated polynuclear complexes, [Et4N]2[{EFe3(CO)9}2Cu2(dppe)] (E = S, 6a; Se, 6b; Te, 6c) and [{EFe3(CO)9}Cu2(dppe)] (E = S, 7a; Se, 7b; Te, 7c), were obtained. Complex 7a could be coordinated with MeCN to form polymer [{SFe3(CO)9}Cu2(dppe)(MeCN)2]n (8a), where the reversible coordination was observed, which was further supported by DFT calculations. [3] [EFe3(CO)9]2− (E = S, Se, Te)─Cu─bpy system When [Et4N]2[SFe3(CO)9] was treated with [Cu(MeCN)4][BF4] and bpy (bpy = 4,4-bipyridine) in various ratios, a series of copper-incorporated polynuclear complexes, [Et4N]2[SFe3(CO)9Cu2(bpy)] ([Et4N]2[1]) and [{SFe3(CO)9}2Cu4(bpy)3(MeCN)2]n (2), were obtained. [Et4N]2[1] can react with [Cu(MeCN)4][BF4] and bpy to form polymer 2.