硫三鐵羰基化合物與第十一族過渡金屬(Cu、Ag)的反應探討
Abstract
[Et4N]2[SFe3(CO)9] 與CuX (X = Cl，Br) 以莫耳比1：5反應，在不同的反應溶劑中會導致不同的產物生成：在THF中得到[{SFe3(CO)9}2Cu4X2]2-；在MeCN中得到 [{SFe3(CO)9}2Cu4X4]4-。另外，將 [Et4N]2[SFe3(CO)9] 與 [Cu(MeCN)4](BF4) 試劑反應：得到 [{SFe3(CO)9}2Cu]3- 和五銅產物 [{SFe3(CO)9}2{Fe(CO)4}2Cu5]3-。
[Et4N]2[SFe3(CO)9] 與 [Cu(MeCN)4](BF4) 和dppx (dppx = dppm或dppe) 反應，依不同比例會生成一系列含銅多核的化合物：[{SFe3(CO)9}Cu2(dppm)(THF)]、[{SFe3(CO)8}Cu2(dppm)2]•THF、[{SFe3(CO)9}Cu2(dppe)] 和 [{SFe3(CO)9}2Cu2(dppe)]2-。其中，化合物 [{SFe3(CO)9}Cu2(dppe)] 藉由溶劑MeCN的配位可形成聚合物 [{SFe3(CO)9}Cu2(dppe)(MeCN)2]n，反應為一可逆的配位重排，可利用DFT理論計算來驗證此結果。
[Et4N]2[SFe3(CO)9] 與 [Ag(MeCN)4](PF6) 和dppx (dppx = dppm或dppe) 反應，依不同比例會生成一系列含銀多核的化合物：雙銀產物 [{SFe3(CO)7}Ag2(dppm)2]、三銀產物 [{SFe3(CO)7}Ag3(dppm)3]+、五銀產物 [{SFe3(CO)7}{Fe(CO)4}Ag5(dppm)3]+ 和化合物 [{SFe3(CO-
)9}2Ag2(dppe)]2-。
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.
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.
Description
Keywords
金屬團簇物