硫三鐵羰基化合物與第十一族過渡金屬(Cu、Ag)的反應探討

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2006

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[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.

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金屬團簇物

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