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Schwartz发现锆氢试剂以来,对烯、炔、双烯等做了广泛的研究.我们曾对羰基化合物、腈及西佛碱的锆氢化反应做了研究.我们又发现从锆氢试剂的光解或热解能获得锆(Ⅲ)配合物.Schwartz等也曾经得到过锆(Ⅲ)配合物.但他们是通过锆(Ⅱ)的氧化·加成得到的. 锆氢试剂,Cp_2Zr(H)Cl,实际上是以氢桥相连的二聚体.量子化学计算数据表明,锆原子带正电荷;氯、氢和Cp(环戊二烯基)配体带负电荷.锆氢试剂在不同反应条件下,有两种不同的Zr-H断裂方式.研究发现:在光或热条件下,与无活泼氢的含氮或磷类配体反应时Zr-H键以均裂方式断裂,产生锆(Ⅲ)活性配合物[Cp_2ZrCl]及氢.其中心原子锆为三价,电
Since the discovery of the zirconium hydride reagent, Schwartz has done extensive research on alkenes, alkynes, diolefins, etc. We have studied the zirconium hydride reaction of carbonyl compounds, nitriles and schiff bases, and we have also found that photolysis from zirconium hydride reagents Or the pyrolytic reaction to obtain the zirconium (III) complexes. Schwartz et al. Also obtained peroxides (III) complexes but they were obtained by the oxidative addition of zirconium (II) .Hydrogen reagents, Cp_2Zr (H) Cl , Which is actually a dimer linked by a hydrogen bridge Quantum chemistry calculations show that the zirconium atom is positively charged and that the chlorine, hydrogen and Cp (cyclopentadienyl) ligands are negatively charged.Zirconium hydride reagents under different reaction conditions , There are two different modes of Zr-H fracture.It is found that under the condition of light or heat, the reaction of Zr-H bond with nitrogenous or phosphorus ligands without active hydrogen cleaves by means of homogeneous cleavage to produce zirconium Ⅲ) active complexes [Cp_2ZrCl] and hydrogen, the central atom of zirconium is trivalent, electricity