H2 activation by zirconaziridinium ions: σ-bond metathesis versus Frustrated Lewis pairs reactivity

Peter Budzelaar; David Hughes; Manfred Bochmann; Alceo Macchioni; Luca Rocchigiani

doi:10.1039/C9CC09466K

H₂ activation by zirconaziridinium ions: σ-bond metathesis versus Frustrated Lewis pairs reactivity

Peter Budzelaar, David Hughes, Manfred Bochmann, Alceo Macchioni, Luca Rocchigiani

Research output: Contribution to journal › Article › peer-review

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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 by 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.

Original language	English
Pages (from-to)	2542-2545
Number of pages	4
Journal	Chemical Communications
Volume	56
Issue number	17
Early online date	17 Jan 2020
DOIs	https://doi.org/10.1039/C9CC09466K
Publication status	Published - 28 Feb 2020

Keywords

CHEMISTRY
COMPLEXES
DIHYDROGEN
HYDROGENATION
INSERTION
METAL
SELF-AGGREGATION TENDENCY
ZIRCONOCENE HYDRIDES

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10.1039/C9CC09466K

Accepted_ManuscriptAccepted author manuscript, 0.99 MB

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title = "H2 activation by zirconaziridinium ions: σ-bond metathesis versus Frustrated Lewis pairs reactivity",

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 by 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.",

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pages = "2542--2545",

journal = "Chemical Communications",

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T1 - H2 activation by zirconaziridinium ions: σ-bond metathesis versus Frustrated Lewis pairs reactivity

AU - Budzelaar, Peter

AU - Hughes, David

AU - Bochmann, Manfred

AU - Macchioni, Alceo

AU - Rocchigiani, Luca

PY - 2020/2/28

Y1 - 2020/2/28

N2 - 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 by 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.

AB - 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 by 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.

KW - CHEMISTRY

KW - COMPLEXES

KW - DIHYDROGEN

KW - HYDROGENATION

KW - INSERTION

KW - METAL

KW - SELF-AGGREGATION TENDENCY

KW - ZIRCONOCENE HYDRIDES

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U2 - 10.1039/C9CC09466K

DO - 10.1039/C9CC09466K

M3 - Article

VL - 56

SP - 2542

EP - 2545

JO - Chemical Communications

JF - Chemical Communications

SN - 1359-7345

IS - 17

ER -

H2 activation by zirconaziridinium ions: σ-bond metathesis versus Frustrated Lewis pairs reactivity

Abstract

Keywords

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Manfred Bochmann

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H₂ activation by zirconaziridinium ions: σ-bond metathesis versus Frustrated Lewis pairs reactivity