Design of Reaction Metal Sites toward Unique Activation of Small Molecules

本研究发现，由配位不饱和钌配合物和二氢衍生的阳离子钌二氢配合物反式-[RuCl (H_2)（二膦）_2]^+与钨二氮配合物顺式-[W (N_2)_2 (PMe_2Ph)_4]在温和条件下反应生成氨。这是第一个利用二氢气将配位二氮转化为氨的例子。硫桥式二钼配合物[(CpMo)_2S(SR)(S_2CH_2)]^+上的二氢气活化以及随后与钨二氮配合物的反应也导致氨的形成。结合氮酶活性位点的结构，建立了从三核到五核的同金属和异金属硫簇的一般合成方法。用这些合理的方法系统地合成了各种含4 -11族金属的同金属、杂双金属和杂三金属硫簇。此外，这些多核配合物被证明可以提供多金属中心，有效地激活和转化小分子的反应活性，如炔烃和烯烃。并且外。

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.