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
Abstract
(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.
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.
Description
Keywords
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