C(spn)−X (n=1–3) Bond Activation by Iron

Małgorzata Bołt; Eveline H. Tiekink; Thomas Hansen; F. Matthias Bickelhaupt; Trevor A. Hamlin

doi:10.1002/ejoc.202201144

C(spⁿ)−X (n=1–3) Bond Activation by Iron

Małgorzata Bołt, Eveline H. Tiekink, Thomas Hansen, F. Matthias Bickelhaupt^*, Trevor A. Hamlin

^*Corresponding author for this work

Research output: Contribution to Journal › Article › Academic › peer-review

Abstract

The iron-catalyzed oxidative addition of C(spⁿ)−X bonds (n=1–3 and X=H, CH₃, Cl) in archetypal model substrates H₃C−CH₂−X, H₂C=CH−X and HC≡C−X to Fe(CO)₄ was investigated using relativistic density functional theory at ZORA-OPBE/TZ2P. The C(spⁿ)−X bonds become substantially stronger going from C(sp³)−X to C(sp²)−X to C(sp)−X, whereas the oxidative addition reaction barrier decreases along this series. Our activation strain and energy decomposition analyses expose that the decreased reaction barrier for the oxidative addition going from sp³ to sp² to sp stems from a relief of the destabilizing (steric) Pauli repulsion between the catalyst and substrate. This originates from the decreasing coordination number of the carbon atom that goes from four in C(sp³)−X to three in C(sp²)−X to two in C(sp)−X. In analogy with our previous results on palladium-catalyzed oxidative additions, this enhances the stabilizing catalyst–substrate interaction, which is able to overcome the more destabilizing strain associated with the stronger C(spⁿ)−X bonds. This work again demonstrates that iron-based catalysts can resemble the behavior of their well-known palladium analogs in the oxidative addition step of cross-coupling reactions.

Original language	English
Article number	e202201144
Pages (from-to)	1-7
Number of pages	7
Journal	European Journal of Organic Chemistry
Volume	2022
Issue number	46
Early online date	9 Nov 2022
DOIs	https://doi.org/10.1002/ejoc.202201144
Publication status	Published - 12 Dec 2022

Bibliographical note

Funding Information:
We thank the Polish National Agency for Academic Exchange (The Bekker NAWA Programme) and the Netherlands Organization for Scientific Research (NWO) for financial support. All DFT calculations were carried out on the Dutch national e-infrastructure with the support of SURF Cooperative.

Funding Information:
We thank the Polish National Agency for Academic Exchange (The Bekker NAWA Programme) and the Netherlands Organization for Scientific Research (NWO) for financial support. All DFT calculations were carried out on the Dutch national e‐infrastructure with the support of SURF Cooperative.

Publisher Copyright:
© 2022 The Authors. European Journal of Organic Chemistry published by Wiley-VCH GmbH.

Funding

We thank the Polish National Agency for Academic Exchange (The Bekker NAWA Programme) and the Netherlands Organization for Scientific Research (NWO) for financial support. All DFT calculations were carried out on the Dutch national e-infrastructure with the support of SURF Cooperative. We thank the Polish National Agency for Academic Exchange (The Bekker NAWA Programme) and the Netherlands Organization for Scientific Research (NWO) for financial support. All DFT calculations were carried out on the Dutch national e‐infrastructure with the support of SURF Cooperative.

Keywords

Activation strain model
Density functional calculations
Homogeneous catalysis
Oxidative addition
Reactivity

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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Cite this

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title = "C(spn)−X (n=1–3) Bond Activation by Iron",

abstract = "The iron-catalyzed oxidative addition of C(spn)−X bonds (n=1–3 and X=H, CH3, Cl) in archetypal model substrates H3C−CH2−X, H2C=CH−X and HC≡C−X to Fe(CO)4 was investigated using relativistic density functional theory at ZORA-OPBE/TZ2P. The C(spn)−X bonds become substantially stronger going from C(sp3)−X to C(sp2)−X to C(sp)−X, whereas the oxidative addition reaction barrier decreases along this series. Our activation strain and energy decomposition analyses expose that the decreased reaction barrier for the oxidative addition going from sp3 to sp2 to sp stems from a relief of the destabilizing (steric) Pauli repulsion between the catalyst and substrate. This originates from the decreasing coordination number of the carbon atom that goes from four in C(sp3)−X to three in C(sp2)−X to two in C(sp)−X. In analogy with our previous results on palladium-catalyzed oxidative additions, this enhances the stabilizing catalyst–substrate interaction, which is able to overcome the more destabilizing strain associated with the stronger C(spn)−X bonds. This work again demonstrates that iron-based catalysts can resemble the behavior of their well-known palladium analogs in the oxidative addition step of cross-coupling reactions.",

keywords = "Activation strain model, Density functional calculations, Homogeneous catalysis, Oxidative addition, Reactivity",

author = "Ma{\l}gorzata Bo{\l}t and Tiekink, {Eveline H.} and Thomas Hansen and Bickelhaupt, {F. Matthias} and Hamlin, {Trevor A.}",

note = "Funding Information: We thank the Polish National Agency for Academic Exchange (The Bekker NAWA Programme) and the Netherlands Organization for Scientific Research (NWO) for financial support. All DFT calculations were carried out on the Dutch national e-infrastructure with the support of SURF Cooperative. Funding Information: We thank the Polish National Agency for Academic Exchange (The Bekker NAWA Programme) and the Netherlands Organization for Scientific Research (NWO) for financial support. All DFT calculations were carried out on the Dutch national e‐infrastructure with the support of SURF Cooperative. Publisher Copyright: {\textcopyright} 2022 The Authors. European Journal of Organic Chemistry published by Wiley-VCH GmbH.",

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AU - Bołt, Małgorzata

AU - Tiekink, Eveline H.

AU - Hansen, Thomas

AU - Bickelhaupt, F. Matthias

AU - Hamlin, Trevor A.

N1 - Funding Information: We thank the Polish National Agency for Academic Exchange (The Bekker NAWA Programme) and the Netherlands Organization for Scientific Research (NWO) for financial support. All DFT calculations were carried out on the Dutch national e-infrastructure with the support of SURF Cooperative. Funding Information: We thank the Polish National Agency for Academic Exchange (The Bekker NAWA Programme) and the Netherlands Organization for Scientific Research (NWO) for financial support. All DFT calculations were carried out on the Dutch national e‐infrastructure with the support of SURF Cooperative. Publisher Copyright: © 2022 The Authors. European Journal of Organic Chemistry published by Wiley-VCH GmbH.

PY - 2022/12/12

Y1 - 2022/12/12

N2 - The iron-catalyzed oxidative addition of C(spn)−X bonds (n=1–3 and X=H, CH3, Cl) in archetypal model substrates H3C−CH2−X, H2C=CH−X and HC≡C−X to Fe(CO)4 was investigated using relativistic density functional theory at ZORA-OPBE/TZ2P. The C(spn)−X bonds become substantially stronger going from C(sp3)−X to C(sp2)−X to C(sp)−X, whereas the oxidative addition reaction barrier decreases along this series. Our activation strain and energy decomposition analyses expose that the decreased reaction barrier for the oxidative addition going from sp3 to sp2 to sp stems from a relief of the destabilizing (steric) Pauli repulsion between the catalyst and substrate. This originates from the decreasing coordination number of the carbon atom that goes from four in C(sp3)−X to three in C(sp2)−X to two in C(sp)−X. In analogy with our previous results on palladium-catalyzed oxidative additions, this enhances the stabilizing catalyst–substrate interaction, which is able to overcome the more destabilizing strain associated with the stronger C(spn)−X bonds. This work again demonstrates that iron-based catalysts can resemble the behavior of their well-known palladium analogs in the oxidative addition step of cross-coupling reactions.

AB - The iron-catalyzed oxidative addition of C(spn)−X bonds (n=1–3 and X=H, CH3, Cl) in archetypal model substrates H3C−CH2−X, H2C=CH−X and HC≡C−X to Fe(CO)4 was investigated using relativistic density functional theory at ZORA-OPBE/TZ2P. The C(spn)−X bonds become substantially stronger going from C(sp3)−X to C(sp2)−X to C(sp)−X, whereas the oxidative addition reaction barrier decreases along this series. Our activation strain and energy decomposition analyses expose that the decreased reaction barrier for the oxidative addition going from sp3 to sp2 to sp stems from a relief of the destabilizing (steric) Pauli repulsion between the catalyst and substrate. This originates from the decreasing coordination number of the carbon atom that goes from four in C(sp3)−X to three in C(sp2)−X to two in C(sp)−X. In analogy with our previous results on palladium-catalyzed oxidative additions, this enhances the stabilizing catalyst–substrate interaction, which is able to overcome the more destabilizing strain associated with the stronger C(spn)−X bonds. This work again demonstrates that iron-based catalysts can resemble the behavior of their well-known palladium analogs in the oxidative addition step of cross-coupling reactions.

KW - Activation strain model

KW - Density functional calculations

KW - Homogeneous catalysis

KW - Oxidative addition

KW - Reactivity

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