硫三鐵羰基化合物與第十一族過渡金屬(Cu、Ag)的反應探討

• Main Author: 朱緯廷
• Other Authors: 謝明惠
• Format: Others
• Language: zh-TW
• Published: 2006
• Online Access: http://ndltd.ncl.edu.tw/handle/84394746361048379257

碩士 === 國立臺灣師範大學 === 化學系 === 94 === When [Et4N]2[SFe3(CO)9] was treated with CuX (X = Cl, Br) in molar ratio of 1:5 in different solvents, two types of products could be obtained. While the reactions of [SFe3(CO)9]2- with CuX (X = Cl, Br) in THF produced [{SFe3(CO)9}2Cu4X2]2-, the reactions in MeCN afforded [{SFe3(CO)9}2Cu4X4]4-. On the other hand, if [Et4N]2[SFe3(CO)9] was treated with [Cu(MeCN)4](BF4), [{SFe3(CO)9}2Cu]3- and the pentacopper complex [{SFe3(CO)9}2{Fe(CO)4}2Cu5]3- were obtained. When [Et4N]2[SFe3(CO)9] was treated with [Cu(MeCN)4](BF4) and dppx (dppx = dppm or dppe) in various ratios, a series of copper-incorporated polynuclear complexes, [{SFe3(CO)9}Cu2(dppm)(THF)], [{SFe3(CO)8}Cu2-(dppm)2]•THF, [{SFe3(CO)9}Cu2(dppe)], and [{SFe3(CO)9}2Cu2(dppe)]2-, were synthesized. Complex [{SFe3(CO)9}Cu2(dppe)] could be coordinated with MeCN to form polymer [{SFe3(CO)9}Cu2(dppe)(MeCN)2]n, in which the reversible coordination mode rearreagement was observed, which was supported by DFT calculations. Further, if [Et4N]2[SFe3(CO)9] was treated with [Ag(MeCN)4](PF6) and dppx (dppx = dppm or dppe) in various ratios, a series of silver-incorporated polynuclear complexes, the disilver complex [{SFe3(CO)7}Ag2(dppm)2], the trisilver complex [{SFe3(CO)7}Ag3(dppm)3]+, the pentasilver complex [{SFe3(CO)7}{Fe(CO)4}Ag5(dppm)3]+, and complex [{SFe3(CO)9}2Ag2(dppe)]2-, were synthesized.