trans-[RuHCl(dppp)2] (6). Free NH3 in 9-16% yields was observed in the reaction mixture, and further NH3 in 36-45% yields was released after base distillation. Detailed studies on the reaction of 5 with numerous Ru(eta 2-H2) complexes showed that the yield of NH3 produced critically depended upon the pKa value of the employed Ru(eta 2-H2) complexes. When 5 was treated with 10 equiv of trans-[RuCl(eta 2-H2)(dppe)2]X
用反式-[RuCl(eta 2-H2)(dppp)2] X(3)(pKa = 4.4)和[RuCl([2])的平衡混合物处理顺-[W(N2)2(PMe2Ph)4](5) dppp)2] X(4)[X = PF6,
BF4或OTf;dppp = 1,3-双(
二苯基膦基)
丙烷],在55℃,1 atm大气压的H2下,于苯
二氯乙烷中含有10当量的基于
钨的Ru原子,历时24 h,得到的NH3的总收率基于
钨的45-55% ,以及反式-[RuHCl(dppp)2](6)的形成。在反应混合物中观察到游离NH 3的产率为9-16%,并且在碱蒸馏后进一步释放NH 3的产率为36-45%。对5与许多Ru(eta 2-H2)配合物的反应进行的详细研究表明,生成的NH3的产率关键取决于所用Ru(eta 2-H2)配合物的pKa值。当用10当量的反式[RuCl(eta 2-H2)(dppe)2] X(8)处理pKa =