| Summary: | 碩士 === 國立臺灣師範大學 === 化學系 === 96 === 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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