含十五族(銻,鉍)與過渡金屬(鉬,鎢)團簇化合物之合成與系統性研究

• Main Author: 張簡宗德
• Other Authors: Minghuey Shieh
• Format: Others
• Language: zh-TW
• Published: 2004
• Online Access: http://ndltd.ncl.edu.tw/handle/22899268240860735415

碩士 === 國立臺灣師範大學 === 化學研究所 === 92 === Abstract [1] Sb-Mo-X (X = Cl, Br, I) / ethyleneglycol system When NaSbO3 and Mo(CO)6 were treated with PPNCl or PPh4Br in refluxing ethyleneglycol / hexane solutions, the halide-bridged tetrahedral compounds [PPN]2[(CO)5MoSbMo3(CO)9(μ-Cl)3] and [PPh4]2[(CO)5Mo- SbMo3(CO)9(μ-Br)3] were obtained, respectively. However, when PPh4I was employed, the mononuclear complex [PPh4]2[Mo(CO)4I2] was yielded. The results indicate the salts can not only provide their cations but also their anions to stabilize the resultant specise. [2] Sb-M (M = Mo,W) / MeOH system When NaSbO3 and Mo(CO)6 were treated with W(CO)6, PPNCl or PPh4Br in refluxing MeOH, the tetrahedron-based antimony-containing methoxide complexes [(CO)5WSbW4(CO)12(μ3-OMe)3]2-, [(CO)5MoSb- Mo4(CO)9Cl3(μ3-OMe)3]2-, and [(CO)5MoSbMo4(CO)12(μ3-OMe)3]2- were produced, respectively. Basically, These compounds each exhibit a SbM3 (M = Mo, W) core geometry with three bridging alkoxy ligands. [3] Bi-Mo / methoxyethanol system If NaBiO3 and Mo(CO)6 were refluxed in methoxyethanol solution, the novel compound [BiMo3(CO)9(μ-OC2H4OMe)3Na]- was afforded, in which the sodium ion is trapped inside the cavity surrounded by three alkoxy groups. When [BiMo3(CO)9(μ-OC2H4OMe)3Na]- reacts with LiCl at room temperature, the ion exchange occurred to form [BiMo3(CO)9- (μ-OC2H4OMe)3Li]-. However, the ion exchange reaction of [BiMo3- (CO)9(μ-OC2H4OMe)3Na]- with K+ was not observed probably due to the size effect.