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

贵金属硫簇合物的合成及其在有机合成中的应用

基本信息

批准号：
06453126
负责人：
HIDAI Masanobui
金额：
$ 4.67万
依托单位：
University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1994
资助国家：
日本
起止时间：
1994 至 1995
项目状态：
已结题

项目摘要

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.

1.硫醇盐桥连的二钌配合物[Cp^*Ru（mu-SPr^i）_2RuCp^*]（1 ; Cp^*=eta^5-C_5Me_5）已被证明可以掺入两个或三个末端炔分子，形成含有钌环核的二钌配合物或通过钌硫环丁烯配合物作为中间体桥连炔配体。还发现，1可以很容易地转化为二钌二烷基配合物，并能催化肼的缩合反应生成N_2和氨。另一方面，用HC@65CFc（Fc=二茂铁基）处理阳离子双钌络合物[Cp^*RuCl（mu-Spr^i）_2RuCp^*] [OTf]（2 ; OTf=OSO_2CF_3）导致形成具有桥连丁烯炔基配体的双钌络合物，其随后被证明是HC@65CFc的二聚和三聚的有效催化剂。此外，还研究了2催化芳醛和三乙基硅烷反应生成1，2-二芳基-1，2-二乙基乙烷.通过[Cp^*RuCl（mu-Cl）_2RuCp^*Cl]与[MS_4] ^的反应，合成了新的以MRu_2（M=W，Mo）为核的金属硫化物混合簇合物<2->。合成了硫醇根桥联的双铱配合物[Cp^*Ir（mu-SPr^i）_2IrCp^*]，并利用该配合物与S_8的反应性，合成了含新型μ-九亚硫基配体的双铱配合物[Cp^*Ir（mu-S_9）（mu-SPr^i）_2IrCp^*].用[（Cp^*Ru）_4（μ_3-Cl）_4]与某些硫化物源反应，合成了一系列硫封端的三钌配合物。簇合物[（Cp^*Ru）_3（mu_3-S）（mu_3-Cl）]与CO反应生成了含有两个或三个桥联CD配体的三钌簇合物. PdMo_3S_4立方烷型簇合物是一种非常优良的催化剂，用于炔与醇和羧酸的反应，均能高收率、高选择性地得到反式加成产物。