Syntheses of Transition Metal-Sulfur Clusters and Development of Their Novel Functions

1.一系列具有两个或三个桥连硫醇配体的双钌配合物，[Cp^*Ru（K-SR）_3RuCp^*] Cl，[Cp^* RuCl（mu-SR）_2RuCp^* Cl]，[Cp^*Ru（mu-SR）_3RuCp^*]和[Cp^*Ru [Cp^* RuCl_2]_2与硫醇化合物反应，得到了（mu-S-i-Pr）_2RuCp^*]（Cp^* = eta^5-C_5Me_5），其结构经X射线衍射分析或EXAFS研究确定。产物的性质与硫醇化合物的性质和反应条件密切相关。同时还研究了它们与CO、t-BuNC和H_2的反应，得到了几种新型的双钌配合物[Cp^*RuCl（mu-SR）_2RuCp^*（L）] Cl、[Cp^*Ru（SR）（mu-SR）_2RuCp^*（L）]、[Cp^*Ru（mu-CO）（mu-SR）_2RuCp^*]和[Cp^*RuH（mu-SR）_2RuCp^*H]（L = CO，t-BuNC）进行了分离和表征.钼硫原子簇[Mo_3S_4（H_2O）_9]^&lt;4+&gt;与钯粉在稀盐酸中反应数天，得到一种新的钯钼硫原子簇[Pd_2Mo_6S_8（H_2O）_<18>]^&lt;8+&gt;。X射线衍射分析表明，PdMo_3S_4为双立方烷结构，两个PdMo_3S_4核之间存在Pd-S桥键。用烯烃如乙烯和1，5-环辛二烯处理该簇在甲醇中的蓝色溶液导致快速颜色变化为红色，而用乙炔如PhC 2 Xi CPh和2-丁炔进行类似处理也得到红色溶液，但要慢得多。甲醇-d_4体系的^1H NMR研究表明，乙烯可能配位在该簇合物的Pd位上.通过[Fe_4S_4（S-t-Bu）_4]^或[Cp ^* RuCl_2]_2与相应的苯二硫醇反应，制备了以间或对苯二硫醇为配体的[Fe_4S_4]^~（2+）或[Cp^* RuCl_2]^~（4+）为核的过渡金属硫聚合物<2->。由这些固体形式的化合物制备的盘显示出包括在半导体的范围内的电导率。

1. A series of diruthenium complexes with two or three bridging thiolate ligands, [Cp^*Ru(K-SR)_3RuCp^*]C1, [Cp^*RuC1(mu-SR)_2RuCp^*C1], [Cp^*Ru(mu-SR)_3RuCp^*], and [Cp^*Ru(mu-S-i-Pr)_2RuCp^*] Were prepared by treatment of [Cp^*RuC1_2]_2 with various thiolate compounds (Cp^* = eta^5-C_5Me_5), the structures of which were determined by the X-ray analyses or the EXAFS study. The products sharply depended upon the nature of the thiolate compounds and reaction conditions. The reactions of these complexes with CO, t-BuNC, and H_2 were also undertaken and several novel diruthenium complexes with CO, t-BuNC, and hydride ligands, [Cp^*RuCl(mu-SR)_2RuCp^*(L)]C1, [Cp^*Ru(SR)(mu-SR)_2RuCp^*(L)], [Cp^*Ru(mu-CO)( mu-SR)_2RuCp^*] and [Cp^*RuH(mu-SR)_2RuCp^*H] (L = CO, t-BuNC) were isolated and characterized.2. The Mo-sulfido cluster [Mo_3S_4(H_2O)_9]^<4+> reacted with Pd powder in diluted hydrochloric acid for several days to give a novel Pd-Mo-sulfido cluster [Pd_2Mo_6S_8(H_2O)_<18>]^<8+>. The double cubane structure with the bridging Pd-S bonds between two PdMo_3S_4 cores was demonstrated by the X-ray analysis. Treatment of the blue solution of this cluster in methanol with olefins such as ethylene and 1,5-cyclooctadiene resulted in the rapid color change to red, whereas analogous treatment with acetylenes such as PhC2 XI CPh and 2-butyne also afforded red solutions but much more slowly. ^1H NMR study in methanol-d_4 disclosed the coordination of ethylene presumably at the Pd site in this cluster.3. Polymeric transition metal-sulfur compounds including [Fe_4S_4]^<2+> or [Cp^*_22Ru_2]^<4+> cores linked by m- or p-benzenedithiolate ligands were prepared by the reactions of [Fe_4S_4(S-t-Bu)_4]^<2-> or [Cp^*RuC1_2]_2 with corresponding benzenedithiols. The disks prepared from these compounds-in'solid form showed the electroconductivities included in the range of those for semiconductors.