Reductive Cleavage of the N−N Bond of Hydrazine Induced by a Cationic Trinuclear Ruthenium Hexahydride Complex, [(Cp‘Ru)3(μ-H)6]X (Cp‘ = η5-C5Me5; X = 1/2 SO4, BF4, PF6, BPh4) and Dihydrogen
Reductive Cleavage of the N−N Bond of Hydrazine Induced by a Cationic Trinuclear Ruthenium Hexahydride Complex, [(Cp‘Ru)3(μ-H)6]X (Cp‘ = η5-C5Me5; X = 1/2 SO4, BF4, PF6, BPh4) and Dihydrogen
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DOI：
10.1021/om0400494
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发表时间：
2004-07
期刊：
影响因子：
2.8
通讯作者：
Y. Nakajima;and Akiko Inagaki;Hiroharu Suzuki
中科院分区：
文献类型：
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作者：
Y. Nakajima;and Akiko Inagaki;Hiroharu Suzuki
单阳离子六氢三Ru[(Cp‘Ru)3(μ-H)6]X(1；X=1/2SO4，BF4，Pf6，BPh4)与肼反应生成单(μ3-亚胺)3(μ3-NH)(μ-H)3(3)和五氢三Ru配合物(Cp’Ru)3(μ3-H)2(μ-H)3(2)。在NH4X或N2H5X存在下，络合物1与2处于平衡状态，并且络合物1在用这样的质子盐处理2后再生。化合物3进一步与肼反应，生成双(μ3-亚胺)配合物(Cp‘Ru)3(μ3-NH)2(μ-H)(4)，这是由质子催化的氮−氮键断裂的结果。3和4都经过加氢反应，与氨一起生成2。因此，在没有添加任何质子源和还原剂的条件下，通过使用单阳离子三核六氢化合物1和二氢实现了联氨的N−氮键的还原断裂。
The reaction of the monocationic triruthenium hexahydride [(Cp‘Ru)3(μ-H)6]X (1; X = 1/2 SO4, BF4, PF6, BPh4) with hydrazine leads to the formation of the mono(μ3-imido) complex (Cp‘Ru)3(μ3-NH)(μ-H)3 (3) and the triruthenium pentahydride complex (Cp‘Ru)3(μ3-H)2(μ-H)3 (2). Complex 1 is in equilibrium with 2 in the presence of NH4X or N2H5X, and complex 1 is regenerated upon treatment of 2 with such a protic salt. Complex 3 further reacts with hydrazine to yield the bis(μ3-imido) complex (Cp‘Ru)3(μ3-NH)2(μ-H) (4) as a result of cleavage of the nitrogen−nitrogen bond, which is formally catalyzed by a proton. Both 3 and 4 undergo hydrogenation to generate 2 together with ammonia. Thus, reductive cleavage of the nitrogen−nitrogen bond of hydrazine leading to ammonia is achieved by the use of the monocationic trinuclear hexahydride complex 1 and dihydrogen under conditions without any added proton source and a reducing agent.