Design of Reaction Metal Sites toward Unique Activation of Small Molecules

研究表明，在温和的条件下，由配位不饱和的Ru(H_2)(双膦)_2形成的阳离子Ruthenitum二氢络合物反式-[RuCl(H_2)(双膦)_2]^+与二氢钨的络合物顺式-[W(N_2)_2(PME_2Ph)_4]反应生成氨。这是第一个利用氢气将配位氮气转化为氨的例子。硫桥化二钼配合物[(CpMo)_2S(SR)(S_2CH_2)]^+上的二氢气体活化也导致了氨的生成。结合固氮酶活性中心的结构，建立了从三核到五核硫簇合物的一般合成方法。通过这些合理的方法，系统地合成了各种含4-11族金属的同、杂、三金属硫化物簇合物。此外，这些多核配合物被证明提供了有效的多金属中心，用于新的活化和转化小分子的反应性，如烯烃。和异氰化物。

The present study revealed that the cationic ruthenitum dihydrogen complexes trans-[RuCl (H_2)(diphosphine)_2]^+ derived from the coordinatively unsaturated ruthenium complexes and dihydrogen react with the tungsten dinitrogen complex cis-[W (N_2)_2 (PMe_2Ph)_4] to afford ammonia under mild conditions. This is the first esample of the transformation of coordinated dinitrogen into ammonia by using dihydrogen gas. Activation of dihydrogen gas on the sulfurbridged dimolybdenum complexes [(CpMo)_2S(SR)(S_2CH_2)]^+ and subsequent reactions with the tungsten dinitrogen complex also led to the formation of ammonia.In connection with the structure of the active site of nitrogenase, general synthetic methods for homo-and heterometallic sulfur clusters ranging from trinuclear to pentanuclear clusters was established. A variety of homo-, heterobi-, and heterotrimetallic sulfido clusters containing group 4 -11 metals were systematically synthesized by these rational approaches. Furthermore, these polynuclear complexes were demonstrated to provide multimetallic centers effective for novel activation and transformation of reactivities of small molecules such as alkynes.alkenes. and isocyanides.