Zirconaziridinium ions [Cp2Zr(η2-CH2NR2)]+ can potentially activate H2 by two routes: σ-bond metathesis or FLP reactivity. We show here that Zr-C hydrogenolysis by σ-bond metathesis precedes and enables subsequent heterolytic H2 cleavage through FLP pathways. DFT calculations show the involvement of transition states with approximately linear N⋯H⋯H and bent Zr⋯H⋯H arrangements without any direct Zr-amine interaction.
H2 activation by zirconaziridinium ions: σ-bond metathesis: Versus frustrated Lewis pair reactivity
Macchioni A.;Rocchigiani L.
2020
Abstract
Zirconaziridinium ions [Cp2Zr(η2-CH2NR2)]+ can potentially activate H2 by two routes: σ-bond metathesis or FLP reactivity. We show here that Zr-C hydrogenolysis by σ-bond metathesis precedes and enables subsequent heterolytic H2 cleavage through FLP pathways. DFT calculations show the involvement of transition states with approximately linear N⋯H⋯H and bent Zr⋯H⋯H arrangements without any direct Zr-amine interaction.File in questo prodotto:
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