Synthesis of Noble Metal-Sulfur Clusters and Their Applications to Organic Synthesis

1.硫代桥联二Ru配合物[Cp^*Ru(Mu-Spr^i)_2RuCp^*](1；Cp^*=eta^5-C_5Me_5)可与两个或三个末端炔烃分子结合，形成含苯环的二Ru络合物或以硫杂环丁烯络合物为中间体桥联炔类配体。研究还发现，1很容易转化为二Ru的二烷基配合物，并且1可以催化肼歧化反应生成N_2和氨。另一方面，阳离子二Ru配合物[Cp^*RuCl(Mu-Spr^i)_2RuCp^*][OTf](2；OTf=OSO_2CF3)与HC@65CFc(FC=二茂铁基)反应生成了具有桥联丁烯配体的二Ru络合物，这是HC@65CFc二聚和三聚反应的有效催化剂。此外，还研究了芳醛和三乙基硅烷催化合成1，2-二芳基-1，2-二硅氧烷的反应。通过[Cp^*RuCl(Mu-Cl)_2RuCp^*Cl]与[MS_4]^&lt；2-&gt；的反应，得到了新的含MRU_2核(M=W，Mo)的混合金属硫化物簇合物。合成了硫代桥联的双Ir络合物[Cp^*Ir(Mu-Spr^i)_2IrCp^*]，并利用这种新的Ir配合物与S_8的反应，合成了一种新的含Mu-非硫磺配体[Cp^*Ir(Mu-S_9)(Mu-Spr^i)_2IrCp^*]的双Ir配合物。用[(Cp^*Ru)_4(Mu_3-Cl)_4]与一定的硫化物源反应，合成了一系列硫化修饰的三Ru配合物。簇合物[(Cp^*Ru)_3(Mu_3-S)(Mu_3-Cl)]与CO反应生成具有两个或三个桥联Cd配体的三Ru簇合物。PdMo_3S_4立方烷型簇合物是一种非常好的催化剂，可用于炔烃与醇和羧酸的反应，两者都提供了高产率和高选择性的反式加成产物。

1. Thiolate-bridged diruthenium complex [Cp^*Ru (mu-SPr^i) _2RuCp^*] (1 ; Cp^*=eta^5-C_5Me_5) has been shown to incorporate two or three molecules of terminal alkynes, forming diruthenium complexes containing ruthenacyclic cores or bridging alkyne ligands via a ruthenathiacyclobutene complex as an intermediate. It has also been found that 1 may readily be converted into diruthenium dialkyl complexes, and that 1 can catalyze the disproportionation reaction of hydrazine into N_2 and ammonia. On the other hand, treatment of the cationic diruthenium complex [Cp^*RuCl (mu-Spr^i) _2RuCp^*] [OTf] (2 ; OTf=OSO_2CF_3) with HC@65CFc (Fc=ferrocenyl) has resulted in the formation of the diruthenium complex having a bridging butenynyl ligand, which has subsequently been shown to be an effective catalyst for di-and trimerization of HC@65CFc. Furthermore, catalytic formations of 1,2-diaryl-1,2-disiloxyethanes from arylaldehydes and triethylsilane using 2 have been demonstrated.2. New mixed metal-sulfide clusters containing MRu_2 core (M=W,Mo) have been prepared from the reactions of [Cp^*RuCl (mu-Cl) _2RuCp^*Cl] with [MS_4] ^<2->.3. Thiolate-bridged diiridium complex [Cp^*Ir (mu-SPr^i) _2IrCp^*] has been prepared and the reactivity of this new Ir complex toward S_8 led to the preparation of a diiridium complex containing a novel mu-nonasulfido ligand [Cp^*Ir (mu-S_9) (mu-SPr^i) _2IrCp^*].4. A series of sulfido-capped triruthenium clucters has been prepared from the reactions of [(Cp^*Ru) _4 (mu_3-Cl) _4] with certain sulfide sources. The cluster [(Cp^*Ru) _3 (mu_3-S) (mu_3-Cl)] proved to react with CO to give the triruthenium clusters with two or three bridging CD ligands.5. The PdMo_3S_4 cubane-type cluster has been shown to be a quite excellent catalyst for the reactions of alkynes with alcohols as well as carboxylic acids, both affording the trans addition products in high yields with high selectivities.