透過 [EFe3(CO)9]2─ (E = Te, Se, S) 與1當量三氯化銻 (SbCl3) 反應生成混合十五族(銻)與十六族(碲、硒、硫)之新穎鐵羰基團簇化合物 [{SbTeFe3(CO)9}{Te2Fe3(CO)9}]– (1), [{SbSeFe3(CO)9}{Se2Fe2(CO)6}]– (2) 與 [{SbSFe3(CO)9}{SFe3(CO)9}]– (3)。化合物 1-3 其結構可視為含[SbEFe3(CO)9] (E = Te, Se, S) 之四角錐型主體，其中的 Sb原子分別外接垂吊的 (pendant) 金屬羰基團簇物片段 [Te2Fe3(CO)9]、[Se2Fe2(CO)6] 及 [SFe3(CO)9]。根據高解析X-ray 電子能譜 (High resolution X-ray Photoelectron Spectroscopy, XPS) 、 X-ray吸收近邊緣結構光譜 (X-ray Absorption Near-Edge Structures, XANES) 發現，化合物 1-3 的 Sb 原子其氧化態為 0。此外，微分脈衝伏安法 (Differential Pulse Voltammetry, DPV) 的測量結果顯示，化合物 1-3 具有擬可逆還原峰位置分別在−0.484、−0.532及−0.586 V（W1/2 = 92、184 及112 mV），暗示化合物 1-3具有還原特性，因此，化合物 1-3 進一步與1當量 [Et4N][HFe(CO)4] 或 [K][HCr(CO)5] 反應時可得到金屬轉移化 (transmetalation) 的產物 [{SbEFe3(CO)9}{M(CO)x}]– (M(CO)x = Fe(CO)4, E = Te, 1-Fe; Se, 2-Fe; S, 3-Fe; M(CO)x = Cr(CO)5, E = Te, 1-Cr; Se, 2-Cr; S, 3-Cr)，化合物 1-M (M = Fe, Cr)、2-M (M = Fe, Cr)、3-M (M = Fe, Cr) 其結構可視為四角錐型主體 [SbEFe3(CO)9] (E = Te, Se, S) 其中的 Sb原子分別外接下垂的 Fe(CO)4、Cr(CO)5 金屬片段。此外，當化合物 2 或 3 與 1 當量 [Et4N][Mn(CO)5] 進行反應時，則產生由 Mn(CO)4 橋接的耳墜型 (earring)化合物 [{SbEFe3(CO)9}2Mn(CO)4]– (E = Se, 2-Mn; S, 3-Mn)。化合物 2-Mn、3-Mn 其結構可視為Mn(CO)4 橋接兩個四角錐型主體 [SbEFe3(CO)9] (E = Se, S)。有趣的是當化合物 1‒3 與競爭試劑 PEt3反應時，高活性之四角錐型化合物 [SbEFe3(CO)9]– (E = Te, Se, S) 可透過高解析液相層析電噴灑游離質譜 (HR-ESI-MS) 測得，顯示 PEt3 相對於 [SbEFe3(CO)9]– (E = Te, Se, S) 有較強的親核性 (Nucleophility) 。最後，本研究也藉由 Density Functional Theory (DFT) 理論計算輔助研究含銻與 16 族元素之金屬團簇化合物 1、2、3、1-M (M = Fe, Cr)、2-M (M = Fe, Cr, Mn)、3-M (M = Fe, Cr, Mn) 之結構、電子特性與光學性質。此系列化合物能隙落於 0.88-1.35 eV，皆具有半導體性質。

A new series of antimony-iron carbonyl chalcogenide clusters, [{SbTeFe3(CO)9}{Te2Fe3(CO)9}]– (1), [{SbSeFe3(CO)9}{Se2Fe2(CO)6}]– (2), and [{SbSFe3(CO)9}{SFe3(CO)9}]– (3), were obtained in moderate yields from the reaction of [EFe3(CO)9]2– (E = Te, Se, S) with 1 equiv. of SbCl3. The structures of complexes 1-3 each can be viewed as a [SbEFe3(CO)9]-based (E = Te, Se, S) square pyramidal cluster with the pendant fragment [Te2Fe3(CO)9], [Se2Fe2(CO)6], and [SFe3(CO)9], respectively. The oxidation state of the bridging Sb atom in each cluster was found to be 0, as evidenced by XPS, XANES and DFT calculations. Differential pulse voltammetry (DPV) measurements indicated that complexes 1-3 underwent quasi-reversible reduction at −0.484, −0.532 and −0.586 V (W1/2 = 92, 184 and 112 mV), respectively, suggesting that complexes 1-3 should have the affinity toward a series of anionic metal fragments. When complexes 1-3 were further treated with 1 equiv. of [Et4N][HFe(CO)4] or [K][HCr(CO)5], the transmetallation products [{SbEFe3(CO)9}{M(CO)x}] (M(CO)x = Fe(CO)4, E = Te, 1-Fe; Se, 2-Fe; S, 3-Fe; M(CO)x = Cr(CO)5, E = Te, 1-Cr; Se, 2-Cr; S, 3-Cr) were obtained as the major products. In addition, when the reaction of complex 2 or 3 with 1 equiv. of [Et4N][Mn(CO)5] was carried out, Mn(CO)4-bridged clusters [{EFe3(CO)9Sb}2Mn(CO)4]– (E = Se, 2-Mn; S, 3-Mn) were synthesized. Complexes 1、2、3、1-M (M = Fe, Cr)、2-M (M = Fe, Cr, Mn)、3-M (M = Fe, Cr, Mn) each can be viewed as a [SbEFe3(CO)9] (E = Te, Se, S) based cluster with the pendant Fe(CO)4/Cr(CO)5 fragment or bridged by the Mn(CO)4 moiety. Preliminary result showed that the naked square pyramidal complex [SbEFe3(CO)9]– (E = Te, Se, S) were unstable and reactive, which was only detected by HR-ESI-MS when complex 1-3 reacted with PEt3. Finally, the structures, electronic and optical properties of these ternary and quaternary antimony-chalcogenide metal carbonyl clusters 1、2、3、1-M (M = Fe, Cr)、2-M (M = Fe, Cr, Mn)、3-M (M = Fe, Cr, Mn) were studied with the aid of DFT calculations.

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