含螯合胺[Cp*Zn(Ln)][BAr4F](2a,Cp*=η3-C5Me5,Ln=N,N,N\',N'-四甲基乙二胺,TMEDA;2b,Ln=N,N,N\',N'-四乙基乙二胺,TEEDA;2c,Cp*=η1-C5Me5,Ln=N,N,N\',N\'\',N\'\'-五甲基-二亚乙基三胺,PMDTA;Ar4F=(3,5-(CF3)2C6H3)4)与二氢反应(约。2bar)在80°C的THF中,得到分子氢化锌阳离子[(Ln)ZnH(thf)m][BAr4F](3a,B,m=1;3c,m=0)先前与Cp*H一起报告关于2b浓度的伪一级动力学表明,Zn-Cp*键对二氢的异相裂解,让人想起σ键复分解。锌阳离子2b在二苯甲酮存在下的氢解得到锌醇盐[(TEEDA)Zn(OCHPh2)(thf)][BAr4F](5b)。显示阳离子2b催化氢化N-亚苄基苯胺。PMDTA络合物2c在乙腈中进行C-H键活化,得到双核μ-κC,κN-氰基甲基锌配合物[(PMDTA)Zn(CH2CN)]2[BAr4F]2(6c)。
Cationic half-sandwich zinc complexes containing chelating amines [Cp*Zn(Ln)][BAr4 F] (2 a, Cp*=η3-C5Me5, Ln=N,N,N\',N\'-tetramethylethylenediamine, TMEDA; 2 b, Ln=N,N,N\',N\'-tetraethylethylenediamine, TEEDA; 2 c, Cp*=η1-C5Me5, Ln=N,N,N\',N\'\',N\'\'-pentamethyldiethylenetriamine, PMDTA; Ar4 F=(3,5-(CF3)2C6H3)4) reacted with dihydrogen (ca. 2 bar) in THF at 80 °C to give molecular zinc hydride cations [(Ln)ZnH(thf)m][BAr4 F] (3 a,b, m=1; 3 c, m=0) previously reported along with Cp*H. Pseudo first-order kinetics with respect to the concentration of 2 b suggests heterolytic cleavage of dihydrogen by the Zn-Cp* bond, reminiscent of σ-bond metathesis. Hydrogenolysis of the zinc cation 2 b in the presence of benzophenone gave the zinc alkoxide [(TEEDA)Zn(OCHPh2)(thf)][BAr4 F] (5 b). Cation 2 b was shown to catalytically hydrogenate N-benzylideneaniline. The PMDTA complex 2 c underwent C-H bond activation in acetonitrile to give a dinuclear μ-κC,κN-cyanomethyl zinc complex [(PMDTA)Zn(CH2CN)]2[BAr4 F]2 (6 c).