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

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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.