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 / Budzelaar, P. H. M.; Hughes, D. L.; Bochmann, M.; Macchioni, A.; Rocchigiani, L.. - In: CHEMICAL COMMUNICATIONS. - ISSN 1359-7345. - 56:17(2020), pp. 2542-2545. [10.1039/c9cc09466k]
H2 activation by zirconaziridinium ions: σ-bond metathesis versus frustrated Lewis pair reactivity
Budzelaar P. H. M.
;
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.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
