Reduction and Synthetic Application of Dinitrogen Mediated by Metal Polyhydrido Clusters

过渡金属簇合物由于相邻金属中心的协同作用而具有显著的反应活性，因此其反应活性一直是人们特别感兴趣的。过渡金属簇合物，特别是金属多配位簇合物，不仅在簇合物的核心有许多氢原子，而且具有在簇合物和配位底物之间转移多个电子的内在性质，在没有质子源和还原剂的情况下，多配位簇合物可能促进氮还原成氨。本研究的主要目的是探讨肼衍生物与金属团簇的反应化学，以阐明过渡金属辅助氮还原的细节。合成含相对路易斯酸金属的异金属簇合物也是本研究的一个重要目标，主要研究结果如下：（1）三钌多配位簇诱导氨的氮-氮键断裂，^[1]（2）三钌多配位簇诱导偶氮苯的氮-氮双键断裂，以及偶氮苯和1，2-二苯基肼的催化氢化，^[2]（3）由阳离子三核钌六氢化物络合物诱导的肼的N-N键的还原断裂，^[3]（4）由钌的三核五氢化物络合物诱导的肼衍生物的N-N键断裂，^[4]（5）含有面封吡啶配体的三核络合物的合成和结构，^[5]（6）三钌簇上的C-N三键断裂，^[6]（7）只含有C_5Me_5作为辅助配体的8- 6族杂三金属多氢化物配合物的合成，^[7]（8）含钌和锇的杂三金属多氢化物配合物的合成及其与乙烯的反应，^[8]（9）含钌和锇的双核和三核多氢化物配合物。^9

The reactivity of transition metal cluster complexes has been of special interest in anticipation of their remarkable reactivity due to the synergy of adjacent metal centers. Transition metal cluster complex, especially, metal polyhydrido cluster not only has many hydrogen atoms in the core of the cluster but also has an intrinsic property of transferring multiple electrons between the cluster and the coordinated substrate, the polyhydrido cluster likely promotes the nitrogen reduction to ammonia in the absence of both a proton source and a reducing agent. The primary aim of this research project was the reaction chemistry of hydrazine derivatives with metal cluster to elucidate details of the transition metal-assisted nitrogen reduction. Synthesis of heterometallic clusters containing a relatively Lewis-acidic metal was also an important object of the research.The main results of the research are as follows : (1) cleavage of nitrogen-nitrogen bonds of ammonia induces by triruthenium polyhydrido clusters, ^1 (2) nitrogen-nitrogen double bond cleavage of azobenzene by a triruthenium polyhydrido complex, and catalytic hydrogenation of azobenzene and 1,2-diphenylhydrazine, ^2 (3) reductive cleavage of the N-N bond of hydrazine induced by a cationic trinuclear ruthenium hexahydrido complex, ^3 (4) nitrogen-nitrogen bond cleavage of hydrazine derivatives by trinuclear pentahydride complex of ruthenium, ^4 (5) synthesis and structure of a trinuclear complex containing a face-capping pyridine ligand, ^5 (6) cleavage of the C -N triple bond on the triruthenium cluster, ^6 (7) synthesis of group 8-group 6 heterotrimetallic polyhydrido complexes having only a C_5Me_5 group as auxiliary ligand, ^7 (8) synthesis and reaction of a heterobimetallic polyhydride complex containing ruthenium and osmium with ethylene, ^8 (9) di- and trinuclear polyhydride complexes containing ruthenium and rhenium. ^9