含銻及硫之過渡金屬 (鉻、鐵、銅) 團簇化合物的合成、轉換關係、化性、物性與理論計算之探討

Group 15 (Sb) or 16 (S)-Containing Transition Metal (Cr, Fe, Cu) Carbonyl Clusters: Synthesis, Transformation, Reactivity, Physical Properties and Computational Studies

孫子硯(Sun Zih-Yan)

指導教授 ： 謝明惠

國立臺灣師範大學/理學院/化學系/碩士(2016年)

https://doi.org/10.6345/NTNU202204292

摘要

['Sb‒Cr 系統
當含氫配子之四面體化合物 [HSb{Cr(CO)5}3]2‒ (1-H) 與 HBF4 進行反應，可形成不飽和平面三角形化合物 [Sb{Cr(CO)5}3]‒ (1)，並伴隨氫氣的產生。有趣的是，利用液態紫外/可見光光譜得知，化合物 1 具有溶劑化顯色特性。將 1 與親核試劑 KX (X = F, Cl, Br, I, OH)、MeLi、NaBH4 反應，可得一系列路易士加成物 [YSb{Cr(CO)5}3]2‒ (Y = F, 1-F; Cl, 1-Cl; Br, 1-Br; I, 1-I; OH, 1-OH; Me, 1-Me; H, 1-H)。此外，當 1 與有機金屬試劑 [HFe(CO)4]‒ 反應，則可得一 [Fe(CO)4]2‒ 片段取代之含氫配子四面體混合鉻鐵化合物 [HSb{Cr(CO)5}2{Fe(CO)4}]2‒ (2-H)。再者，當 2-H 進行去質子化反應時，可形成不飽和平面三角形化合物 [Sb{Cr(CO)5}2{Fe(CO)4}]‒ (2) 與雙 [Fe(CO)4]2‒ 片段橋接兩個 Sb 之混合鉻鐵產物 [HOSb2{Cr(CO)5}3{Fe(CO)4}2]‒ (3)。最後，藉由電化學、液態以及固態反射式紫外/可見光光譜與 X-ray 吸收近邊緣結構光譜 (XANES)，並搭配理論計算來探討此系列化合物之合成、氧化還原行為、光學性質與電子結構特性。

S‒Fe‒Cu 系統
利用 [SFe3(CO)9Cu2(MeCN)2] (1) 與含氮配子 4,4’-dipyridine (dpy)、1,2-bis(4-dipyridyl)ethane (bpea)、4,4’-trimethylenedipyridine (bpp) 進行溶劑輔助研磨 (liquid-assisted grinding, LAG) 反應，可計量形成一系列混合鐵銅羰基之新穎一維聚合物 [SFe3(CO)9Cu2(dpy)3]n (3) 和 [SFe3(CO)9Cu2(bpea)]n (4) 及二維聚合物 [SFe3(CO)9Cu2(MeCN)(dpy)1.5]n (2)、[SFe3(CO)9Cu2(bpea)2]n (5) 與 [SFe3(CO)9Cu2(bpp)2]n (6)。藉由固態反射式光譜可得知此系列聚合物其能隙範圍為 1.44‒1.80 eV，皆具有半導體性質。另外，此系列 S‒Fe‒Cu 聚合物之合成、轉換關係及 Cu 金屬氧化態則藉由 X 光粉末繞射儀 (PXRD)、高解析 X 光電子能譜 (XPS) 與 X 光吸收近邊緣結構光譜 (XANES) 進一步驗證。

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關鍵字

銻 ； 鉻 ； 硫 ； 鐵 ； 銅

並列摘要

['Sb‒Cr system
The unsaturated trigonal-planar stibinidene [Sb{Cr(CO)5}3]– (1) was synthesized from the reaction of the tetrahedral hydride complex [HSb{Cr(CO)5}3]2– (1-H) with HBF4, accompanied with the generation of hydrogen. Interestingly, complex 1 exhibited the solvatochromic properties, detected by UV/Vis spectra. The reactions of 1 with different nucleophiles, KX (X = Cl, Br, I, OH), MeLi, and NaBH4, led to the formation of a series of tetrahedral Lewis adducts [YSb{Cr(CO)5}3]2– (Y = F, 1-F; Cl, 1-Cl; Br, 1-Br; I, 1-I; OH, 1-OH; Me, 1-Me; H, 1-H). Moreover, when complex 1 reacted with the organometallic reagent [HFe(CO)4]–, the tetrahedral monosubstituted hydride-containing product [HSb{Cr(CO)5}2{Fe(CO)4}]2– (2-H) was obtained. In addition, when complex 2-H was treated with HBF4, the unsaturated trigonal-planar mixed chromium-iron carbonyl complex [Sb{Cr(CO)5}2{Fe(CO)4}]‒ (2) and Fe(CO)4-bridged dinuclear antimony complex [HOSb2{Cr(CO)5}3{Fe(CO)4}2]‒ (3) were produced. Finally, the synthesis, electrochemistry, UV-Vis absorption, diffuse reflectance spectra, and X-ray absorption near edge structure (XANES) of these Sb‒Cr complexes were studied with the aid of DFT calculations.
S‒Fe‒Cu system
When [SFe3(CO)9Cu2(MeCN)2] (1) was treated with stoichiometric 4,4’-dipyridine (dpy), 1,2-bis(4-dipyridyl)ethane (bpea), and 4,4’-trimethylenedipyridine (bpp) via liquid-assisted grinding (LAG) method, a new series of organometallic-organic hybrid polymers, namely, two 1D polymers [SFe3(CO)9Cu2(MeCN)(dpy)1.5]n (2) and [SFe3(CO)9Cu2(bpea)]n (4) and three 2D polymers [SFe3(CO)9Cu2(dpy)3]n (3), [SFe3(CO)9Cu2(bpea)2]n (5), and [SFe3(CO)9Cu2(bpp)2]n (6), were obtained quantitatively. Moreover, the diffuse reflectance spectra showed that 2-6 had semiconducting behaviors with energy gaps in the range of 1.44‒1.80 eV. In addition, the formation, transformation, and oxidation state of Cu atom of these polymers were elucidated by powder X-ray diffraction (PXRD), X-ray photonelectron spectroscopy (XPS), and X-ray absorption near edge structure (XANES) analyses.

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並列關鍵字

antimony ； chromium ； sulfur ； iron ； copper

參考文獻

第一章

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