Understanding the differences between iron and palladium in cross-coupling reactions

Xiaobo Sun; Marcus V.J. Rocha; Trevor A. Hamlin; Jordi Poater; F. Matthias Bickelhaupt

doi:10.1039/c8cp07671e

Understanding the differences between iron and palladium in cross-coupling reactions

Xiaobo Sun, Marcus V.J. Rocha, Trevor A. Hamlin, Jordi Poater, F. Matthias Bickelhaupt^*

^*Corresponding author for this work

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Abstract

We aim at developing design principles, based on quantum chemical analyses, for a novel type of iron-based catalysts that mimic the behavior of their well-known palladium analogs in the bond activation step of cross coupling reactions. To this end, we have systematically explored C-X bond activation via oxidative addition of CH ₃ X substrates (X = H, Cl, CH ₃ ) to model catalysts ^m Fe(CO) ₄ ^q (q = 0, -2; m = singlet, triplet) and, for comparison, Pd(PH ₃ ) ₂ and Pd(CO) ₂ , using relativistic density functional theory at the ZORA-OPBE/TZ2P level. We find that the neutral singlet iron catalyst ¹ Fe(CO) ₄ activates all three C-X bonds via barriers that are lower than those for Pd(PH ₃ ) ₂ and Pd(CO) ₂ . This is a direct consequence of the capability of the iron complex to engage not only in π-backdonation, but also in comparably strong σ-donation. Interestingly, whereas the palladium complexes favor C-Cl activation, ¹ Fe(CO) ₄ shows a strong preference for activating the C-H bond, with a barrier as low as 10.4 kcal mol ^-1 . Our results suggest a high potential for iron to feature in palladium-type cross-coupling reactions.

Original language	English
Pages (from-to)	9651-9664
Number of pages	14
Journal	Physical Chemistry Chemical Physics
Volume	21
Issue number	19
Early online date	25 Feb 2019
DOIs	https://doi.org/10.1039/c8cp07671e
Publication status	Published - 21 May 2019

Funding

We thank the China Scholarship Council (CSC), the Ministry of Education of Brazil/CAPES (1938/14-2), the Spanish MINECO (CTQ2016-77558-R and MDM-2017-0767), the Generalitat de Catalunya (2017SGR348), and the Netherlands Organization for Scientific Research (NWO) for financial support.

Funders	Funder number
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior	1938/14-2
Generalitat de Catalunya	2017SGR348
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
Ministerio de Economía y Competitividad	CTQ2016-77558-R, MDM-2017-0767
China Scholarship Council
Ministério da Educação

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Understanding the differences between iron and palladium in crosscoupling reactionsFinal published version, 4.93 MBLicence: Article 25fa Dutch Copyright Act

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title = "Understanding the differences between iron and palladium in cross-coupling reactions",

abstract = " We aim at developing design principles, based on quantum chemical analyses, for a novel type of iron-based catalysts that mimic the behavior of their well-known palladium analogs in the bond activation step of cross coupling reactions. To this end, we have systematically explored C-X bond activation via oxidative addition of CH 3 X substrates (X = H, Cl, CH 3 ) to model catalysts m Fe(CO) 4 q (q = 0, -2; m = singlet, triplet) and, for comparison, Pd(PH 3 ) 2 and Pd(CO) 2 , using relativistic density functional theory at the ZORA-OPBE/TZ2P level. We find that the neutral singlet iron catalyst 1 Fe(CO) 4 activates all three C-X bonds via barriers that are lower than those for Pd(PH 3 ) 2 and Pd(CO) 2 . This is a direct consequence of the capability of the iron complex to engage not only in π-backdonation, but also in comparably strong σ-donation. Interestingly, whereas the palladium complexes favor C-Cl activation, 1 Fe(CO) 4 shows a strong preference for activating the C-H bond, with a barrier as low as 10.4 kcal mol -1 . Our results suggest a high potential for iron to feature in palladium-type cross-coupling reactions. ",

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AU - Poater, Jordi

AU - Matthias Bickelhaupt, F.

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AB - We aim at developing design principles, based on quantum chemical analyses, for a novel type of iron-based catalysts that mimic the behavior of their well-known palladium analogs in the bond activation step of cross coupling reactions. To this end, we have systematically explored C-X bond activation via oxidative addition of CH 3 X substrates (X = H, Cl, CH 3 ) to model catalysts m Fe(CO) 4 q (q = 0, -2; m = singlet, triplet) and, for comparison, Pd(PH 3 ) 2 and Pd(CO) 2 , using relativistic density functional theory at the ZORA-OPBE/TZ2P level. We find that the neutral singlet iron catalyst 1 Fe(CO) 4 activates all three C-X bonds via barriers that are lower than those for Pd(PH 3 ) 2 and Pd(CO) 2 . This is a direct consequence of the capability of the iron complex to engage not only in π-backdonation, but also in comparably strong σ-donation. Interestingly, whereas the palladium complexes favor C-Cl activation, 1 Fe(CO) 4 shows a strong preference for activating the C-H bond, with a barrier as low as 10.4 kcal mol -1 . Our results suggest a high potential for iron to feature in palladium-type cross-coupling reactions.

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Understanding the differences between iron and palladium in cross-coupling reactions

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