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

1.通过[Cp^*Ru(K-SR)_3RuCp^*][Cp^*Ru(K-SR)_3RuCp^*][Cp^*Ru(Mu-SR)_2RuCp^*C1]、[Cp^*Ru(Mu-SR)_3RuCp^*]和[Cp^*Ru(Mu-S-i-Pr)_2RuCp^*]与不同的硫酸盐化合物(Cp^*Ru(K-SR)_3RuCp^*][Cp^*Ru(Mu-SR)_2RuCp^*][Cp^*Ru(Mu-SR)_3RuCp^*][Cp^*Ru(Mu-SR)_3RuCp^*][Cp^*Ru(K-SR)_3RuCp^*][Cp^*Ru(Mu-SR)_2RuCp^*][Cp^*=ETA^*=ETA^5-C_5Me_5]处理[Cp^*Ru(K-SR)_3RuCp^*]，[Cp^*Ru(Mu-SR)_3RuCp^*]，[Cp^*Ru(Mu-SR)_3RuCp^*]产物主要取决于硫酸盐化合物的性质和反应条件。这些配合物还与CO、t-BuNC和H_2反应，得到了几个新的与CO、t-BuNC和氢化物配体的二Ru配合物，[Cp^*Ru(Mu-SR)_2RuCp^*(L)]C1，[Cp^*Ru(Sr)(Mu-SR)_2RuCp^*(L)]，[Cp^*Ru(Mu-CO)(Mu-SR)_2RuCp^*]和[Cp^*Reh(Mu-SR)_2RuCp^*H](L=CO，t-BuNC)。钼硫簇合物[Mo_3S_4(H_2O)_9]^&lt；4&gt；与Pd粉在稀盐酸中反应数天，得到一种新型的钯钼硫簇合物[Pd_2Mo_6S_8(H_2O)_8(H_2O)_t；18&gt；]^&lt；8&gt；。X-射线分析表明，PdMo3S4为双立方结构，Pd-S键为桥联结构。该簇的蓝色溶液在甲醇中与烯烃(如乙烯和1，5-环辛二烯)处理后迅速变成红色，而用乙炔(如PhC2 XI CPH和2-丁炔)类似的处理也得到红色溶液，但速度要慢得多。在甲醇-d_4中的~1H核磁共振研究揭示了乙烯可能在该簇中的Pd中心配位。通过[Fe4S4(S-t-Bu)4]^&lt；2-&gt；或[Cp^**RuCl2]_2与相应的苯二硫醇反应，合成了含[Fe4S4]^&lt；2&gt；或[Cp^**Ru2]^&lt；4&gt；核的间或对苯二硫酚连接的聚合物过渡金属硫化合物。由这些固体形式的化合物制备的圆盘显示出包括在半导体的导电率范围内的电导性。

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.