H2 activation by zirconaziridinium ions: σ-bond metathesis versus frustrated Lewis pair reactivity

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...

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Bibliographic Details
Published in:Chemical communications (Cambridge, England) England), 2020-02, Vol.56 (17), p.2542-2545
Main Authors: Budzelaar, Peter H M, Hughes, David L, Bochmann, Manfred, Macchioni, Alceo, Rocchigiani, Luca
Format: Article
Language:English
Subjects:
Crystallography
Ductile-brittle transition
Hydrogenolysis
Mathematical analysis
Metathesis
Zirconium
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Summary: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.
ISSN:1359-7345
1364-548X
DOI:10.1039/c9cc09466k