含主族元素 (硫、鉍) 之過渡金屬 (鉻、錳、鉬) 團簇化合物的合成、化性與物性研究

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2014

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(1) Bi─Mo 系統 將 [BiMo3(CO)9(μ-OC2H4OCH3)3Na]─ (1) 與一系列鹼土金屬氯化物 (MgCl2、CaCl2、SrCl2、BaCl2˙2H2O) 於 MeCN 或 THF 下進行離子交換反應得到一系列以 OC2H4OCH3 為配基之鉍三鉬羰基含鹼土金屬離子團簇化合物 BiMo3(CO)9(μ-OC2H4OCH3)3ML (ML = Mg, 2; Ca(NCMe)2, 3a; Ca(DMF)2, 3b; Sr(C3H6O)2, 4c) 及藉由羰基配位所形成之聚合物 [BiMo3(CO)9(μ-OC2H4OCH3)3ML]n (ML = Sr(NCMe), 4a; Sr(OH2), 4b; Ba(NCMe)(OH2), 5),進一步利用機械研磨方式探討 4a、4b 以及 4c 三者間固態之轉換關係。本研究以電化學、電子吸收光譜以及核磁共振光譜等方法,探究化合物 2、3a、3b 以及 4c 與聚合物 4a、4b 以及 5 之鹼土金屬陰電性效應與聚合效應。進一步藉由 NMR 滴定實驗比較鹼金屬 (Li+、K+)、鹼土金屬 (Mg2+、Ca2+、Sr2+、Ba2+)、過渡金屬 (Zn2+、Cd2+) 以及主族金屬 (Tl+、Sn2+、Pb2+) 離子置換化合物 1中 Na+ 離子能力。 (2) E─Cr (E = S, Se, Te) 系統 將含氫配子之雙三角錐化合物 [HS2Cr3(CO)9]3─ (1) 分別與醯氯類 (PhCOCl、CH3(CH2)2COCl) 試劑以及鹵烷類試劑 (CH3(CH2)4Br、CH3(CH2)5Br) 於 MeCN 反應,分別形成雙三角錐化合物 [S2Cr3(CO)10]2─ (2a) 與雙蝴蝶構型之 [{S2Cr2(CO)7}2Cr]3─ (3),其中化合物 1 與醯氯類試劑反應,可得到醛類產物 (PhCOH、CH3(CH2)2COH)。再者,化合物 1 與兩當量金屬試劑 Mn(CO)5Br 於 KOH 鹼性條件下反應,可形成混和錳鉻之羰基化合物 [S2Cr3(CO)10{Mn(CO)5}2]2─ (4) 和化合物 2a。化合物 4 以金字塔構型 S2Cr3 為主體,於每一個 S 原子端接 Mn(CO)5 片段。進一步藉由電化學以及電子吸收光譜探討 S─Cr 系列化合物同核或異核擴核性應以及相關雙三角錐構型之 [E2Cr3(CO)10]2─ (E = S、Se、Te) 之主族效應,並搭配理論計算佐證。
The metathesis recation of [BiMo3(CO)9(μ-OC2H4OCH3)3Na]─ (1) with a series of alkaline earth metal−chloride complexation (MgCl2、CaCl2、SrCl2、BaCl2˙2H2O) in MeCN or THF solution to form a series of the BiMo3(CO)9-based with three methoxyethanol ligands bound to alkaline earth metal ion clusters BiMo3(CO)9(μ-OC2H4OCH3)3ML (ML = Mg, 2; Ca(NCMe)2, 3a; Ca(DMF)2, 3b; Sr(OC3H6)2, 4a) and 1D zigzag polymeric cluster [BiMo3(CO)9(μ-OC2H4OCH3)3ML]n (ML = Sr(NCMe), 4a; Sr(OH2), 4b; Ba(NCMe)(OH2), 5) were produced. Polymers 4a, 4b and 5 consisted of the BiMo3(CO)9 unit linked by the O atom of the CO in one unit to the Sr or Ba atom of the adjacent one, to form 1D zigzag structure. Furthermore, mechanochemical solid-state transformation among clusters 4a, 4b, and 4c. Moreover, The NMR, electron absorptions measurements, and electrochemistry of clusters 2-5 were discussed in term of metal electronegativity and polymerization effect. On the other hand, the metalation of cluster 1 with a series of metal cations (Li+, K+, Mg2+, Ca2+, Sr2+, Ba2+, Zn2+, Cd2+, Tl+, Sn2+, Pb2+) was investigated by 1H NMR titration. Trigonal-bipyramidal carbonyl hydride cluster [HS2Cr3(CO)9]3– (1) with acyl chloride RCOCl (R = Ph, CH3(CH2)2) or alkyl bromide RBr (R = CH3(CH2)4, CH3(CH2)5) in MeCN led to the TBP cluster [S2Cr3(CO)10]2– (2a) and the Cr-linked S2Cr2(CO)-based cluster [Cr{S2Cr2(CO)7}2]3– (3), respectivity, and the reactions of cluster 1 with RCOCl yielded aldehyde RCOH. Further studies showed that 1 with 2 eqiv of Mn(CO)5Br in MeCN to produce mixed Mr-Cr sulfide carbonyl cluster [S2Cr3(CO)10{Mn(CO)5}2]2─ (4) and 2a, the dianionic cluster 4 was shown to display a S2Cr3 square-pyramidal core with each S atom externally coordinated by one Mn(CO)5 group. Moreover, The electron absorptions measurements, and electrochemistry of clusters 1─4 were studied in term of cluster expansion effect and chalcogenide effect, which were elucidated by molcular orbital calculations of density functional theory.

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金屬團簇化合物, 離子交換反應, 混合金屬, 機械研磨, 磁性, metal cluster, ion exchange reaction, mixed metal, mechanochemical reaction, magnetism

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