含主族元素(銻、鉍、碲)與過渡金屬(鉬、釕)團簇化合物的合成與其反應探討及化性研究
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2008
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1. Sb-Mo-CO系統化合物之合成
[PPN]2[(CO)5MoSbMo3(CO)9(-Cl)3]與HOC2H4OMe、HOC2H4CH(Me)-
OMe及HOC3H6OMe在鹼性條件下反應，利用醇類有機溶劑取代結構中的三個-Cl，分別可得[PPN][SbMo3(CO)9(-OC2H4OMe)3Na]、[PPN][(CO)5MoSbMo3(CO)9(-OC3H6OMe)3K]與[PPN][(CO)5MoSbMo3(CO)9(-OC2H4CH(Me)OMe)3K]。所形成的結構具有捕捉陽離子的特性；除此之外，藉由選擇不同碳鏈的醇類有機溶劑可以改變捕捉陽離子的選擇性。
2. Te-Ru-CO系統化合物之合成
利用K2TeO3與Ru3(CO)12在MeOH溶劑中加熱反應，可以獲得產物[PPh4][HTeRu3(CO)9]、[PPh4][HTe2Ru4(CO)10]、[PPh4]2[Te2Ru4(CO)10]與[PPh4]2[Te4Ru8(CO)19]一系列的化合物，由反應的過程可以觀察到Te-Ru系統產物的不穩定性；除此之外，利用一鍋化的反應方式引入[Cu(MeCN)4]BF4，可以獲得具有孔洞特性及半導體性質的聚合物{[PPh4]2[Te2Ru4(CO)10Cu4Br2(-Br)2]•0.75CH2Cl2}∞。若是以非一鍋化的方式，利用[PPh4]2[Te2Ru4(CO)10Cu2Br2]直接與[Cu(MeCN)4]BF4反應，則可得一中性化合物[Te2Ru4(CO)10{Cu3Br2(MeCN)3}2]，同時藉由DFT理論計算來佐證實驗上獲得的結果。
1. Sb-Mo-CO system The reaction of [PPN]2[(CO)5MoSbMo3(CO)9(-Cl)3] with HOC2H4OMe, HOC3H6OMe or HOC2H4CH(Me)OMe in a basic solution produced the novel tetrahedral clusters [PPN][SbMo3(CO)9(-OC2H4OMe)3Na], [PPN][(CO)5MoSb- Mo3(CO)9(-OC3H6OMe)3K], and [PPN][(CO)5MoSbMo3(CO)9(-OC2H4CH(M- e)OMe)3K], respectively. The cations, Na+ and K+, were caught in these structures to form ion-capsulated structures. In addition, the selectivities of cations were controlled by increasing the chain of the alcohols. 2. Te-Ru-CO system The reaction of K2TeO3 with Ru3(CO)12 in a methanol solution produced a series of poynuclear complexes, [PPh4][HTeRu3(CO)9], [PPh4][HTe2Ru4(CO)10], [PPh4]2[Te2Ru4(CO)10], and [PPh4]2[Te4Ru8(CO)19]. However, these complexes were unstable compared with the analogus complexes in the Se-Ru-CO system. Additionally, the reaction mixture of K2TeO3 and [Ru3(CO)12] was treated with PPh4Br followed by the addition of [Cu(MeCN)4]BF4, the -Cu(Br)CuBr-bridged Te2Ru4-based octahedral cluster chain polymer {[PPh4]2[Te2Ru4(CO)10Cu4Br2(- Br)2]•0.75CH2Cl2}∞ was produced. When the complex [PPh4]2[Te2Ru4(CO)10C- u2Br2] was treated with [Cu(MeCN)4]BF4, the product [Te2Ru4(CO)10{Cu3Br2(Me- CN)3}2] was obtained. The formation of these clusters were further examined by molecular orbital calculations at the B3LYP level of density functional theory.
1. Sb-Mo-CO system The reaction of [PPN]2[(CO)5MoSbMo3(CO)9(-Cl)3] with HOC2H4OMe, HOC3H6OMe or HOC2H4CH(Me)OMe in a basic solution produced the novel tetrahedral clusters [PPN][SbMo3(CO)9(-OC2H4OMe)3Na], [PPN][(CO)5MoSb- Mo3(CO)9(-OC3H6OMe)3K], and [PPN][(CO)5MoSbMo3(CO)9(-OC2H4CH(M- e)OMe)3K], respectively. The cations, Na+ and K+, were caught in these structures to form ion-capsulated structures. In addition, the selectivities of cations were controlled by increasing the chain of the alcohols. 2. Te-Ru-CO system The reaction of K2TeO3 with Ru3(CO)12 in a methanol solution produced a series of poynuclear complexes, [PPh4][HTeRu3(CO)9], [PPh4][HTe2Ru4(CO)10], [PPh4]2[Te2Ru4(CO)10], and [PPh4]2[Te4Ru8(CO)19]. However, these complexes were unstable compared with the analogus complexes in the Se-Ru-CO system. Additionally, the reaction mixture of K2TeO3 and [Ru3(CO)12] was treated with PPh4Br followed by the addition of [Cu(MeCN)4]BF4, the -Cu(Br)CuBr-bridged Te2Ru4-based octahedral cluster chain polymer {[PPh4]2[Te2Ru4(CO)10Cu4Br2(- Br)2]•0.75CH2Cl2}∞ was produced. When the complex [PPh4]2[Te2Ru4(CO)10C- u2Br2] was treated with [Cu(MeCN)4]BF4, the product [Te2Ru4(CO)10{Cu3Br2(Me- CN)3}2] was obtained. The formation of these clusters were further examined by molecular orbital calculations at the B3LYP level of density functional theory.
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團簇物