第十六族元素(S、 Se、 Te)混合錳與鐵及鉛鐵之金屬團簇化合物的合成及其相關性研究

鄭尹威(YiWei Cheng)

指導教授 ： 謝明惠

國立臺灣師範大學/理學院/化學系/碩士(2001年)

摘要

[Et4N]2[PbFe3(CO)12]與C3H5Br的反應，於室溫反應14小時後，得到中性產物Fe2(CO)9。而與含金屬親電子性試劑Mn(CO)5Br的反應，在氰甲烷溶液加熱迴流6天後，則可獲得雙三角錐結構產物[Et4N]2[Pb2Fe5(CO)17]。
[Et4N]2[Pb{Fe(CO)4}2{Fe2(CO)8}]與HBF4的反應，於室溫反應4天，最後得[Et4N]2[Pb2Fe5(CO)17]及紅色[Et4N][HFe2(CO)8]；在與CH3COCl得反應中，室溫攪拌4天後，則只能得到[Et4N][HFe2(CO)8]化合物；與AgNO3反應中，在室溫反應3天後，得到含”μ3-OH ”產物[Et4N][Fe3(CO)9(μ3-OH)]；最後在與Mn(CO)5Br/AgBF4反應，於低溫 (-50 ℃) 中則可得到藍色三角形Mn-Fe化合物[Et4N][MnFe2(CO)12]。
含第16族元素(S、Se、Te)於6.5 M 的KOH/MeOH溶液中與Mn2(CO)10及Fe(CO)5反應，反應時間S (4天)、Se (5天)、Te (7天)後收反應，利用[PPN]+ 為陽離子，令人訝異得到相同結構四角錐產物[E2Mn2Fe(CO)9]2- (E = S、Se、Te)，電子計算都符合18電子計算規則。
將[E2Mn2Fe(CO)9]2- (E = S、Se、Te)與[Cu(CH3CN)4][BF4]反應時， [E2Mn2Fe(CO)9]2- (E = S、Se)則會斷鍵重排得到紫色八面體結構之[PPN][E2Mn3Fe(CO)12] (E = S、Se)。

關鍵字

硫 ； 硒 ； 碲

並列摘要

Reaction of [Et4N]2[PbFe3(CO)12] with C3H5Br at room temperature for 14 hours produced the netural complex Fe2(CO)9. When [Et4N]2[PbFe3(CO)12] reacts with Mn(CO)5Br in refluxing CH3CN solution for 6 days, the trigonal bipyramidal cluster [Et4N]2[Pb2Fe5(CO)17] was obtained.
If [Et4N]2[Pb{Fe(CO)4}2{Fe2(CO)8}] reacted with HBF4 at room temperature after 4 days, the trigonal bipyramidal cluster [Et4N]2[Pb2Fe5(CO)17] and the red compound [Et4N][HFe2(CO)8] could be afforded. Furthermore, the reaction of [Et4N]2[Pb{Fe(CO)4}2{Fe2(CO)8}] with CH3COCl at room temperature for 4 days, the known complex [HFe2(CO)8]－ was produced. When [Et4N]2[Pb{Fe(CO)4}2{Fe2(CO)8}] were treated with AgNO3 at room temperature for 3 days, the cluster [Et4N][Fe3(CO)9(μ3-OH)] with μ3-OH was produced. Finally, the reaction of [Et4N]2[Pb{Fe(CO)4}2{Fe2(CO)8}] with Mn(CO)5Br/AgBF4 gave the trigonal-planar compound [Et4N][Fe2Mn(CO)12].
When S, Se, or Te powder was added into the mixture of Mn2(CO)10 and Fe(CO)5 in 6.5 M KOH/MeOH solution followed by the precipitation with [PPN]Cl, the clusters [PPN]2[E2FeMn2(CO)9] (E = S, Se, Te) were produced. Three complexes display the E2FeMn2 square pyramidal geometry, which obeys the EAN Rule.
If the mixed-metal clusters [PPN]2[E2Mn2Fe(CO)9] (E = S, Se, Te) were further treated with [Cu(CH3CN)4][BF4], [PPN]2[E2Mn2Fe(CO)9] (E = S, Se) would undergo bond-cleavage and formation processes to produce the purple complexes [PPN][E2Mn3Fe(CO)12] (E = S, Se).

並列關鍵字

Sulfur ； Selenium ； Tellurium