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

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

12 Citations (Scopus)

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 CH₃X substrates (X = H, Cl, CH₃) to model catalysts ^mFe(CO)₄^q (q = 0, -2; m = singlet, triplet) and, for comparison, Pd(PH₃)₂ and Pd(CO)₂, using relativistic density functional theory at the ZORA-OPBE/TZ2P level. We find that the neutral singlet iron catalyst ¹Fe(CO)₄ activates all three C-X bonds via barriers that are lower than those for Pd(PH₃)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, ¹Fe(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
DOIs	https://doi.org/10.1039/c8cp07671e
Publication status	Published - 2019
Externally published	Yes

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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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 CH3X substrates (X = H, Cl, CH3) to model catalysts mFe(CO)4q (q = 0, -2; m = singlet, triplet) and, for comparison, Pd(PH3)2 and Pd(CO)2, using relativistic density functional theory at the ZORA-OPBE/TZ2P level. We find that the neutral singlet iron catalyst 1Fe(CO)4 activates all three C-X bonds via barriers that are lower than those for Pd(PH3)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, 1Fe(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.",

author = "Xiaobo Sun and Rocha, \{Marcus V.J.\} and Hamlin, \{Trevor A.\} and Jordi Poater and \{Matthias Bickelhaupt\}, F.",

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AU - Sun, Xiaobo

AU - Rocha, Marcus V.J.

AU - Hamlin, Trevor A.

AU - Poater, Jordi

AU - Matthias Bickelhaupt, F.

N1 - Publisher Copyright: © the Owner Societies 2019.

PY - 2019

Y1 - 2019

N2 - 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 CH3X substrates (X = H, Cl, CH3) to model catalysts mFe(CO)4q (q = 0, -2; m = singlet, triplet) and, for comparison, Pd(PH3)2 and Pd(CO)2, using relativistic density functional theory at the ZORA-OPBE/TZ2P level. We find that the neutral singlet iron catalyst 1Fe(CO)4 activates all three C-X bonds via barriers that are lower than those for Pd(PH3)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, 1Fe(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.

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 CH3X substrates (X = H, Cl, CH3) to model catalysts mFe(CO)4q (q = 0, -2; m = singlet, triplet) and, for comparison, Pd(PH3)2 and Pd(CO)2, using relativistic density functional theory at the ZORA-OPBE/TZ2P level. We find that the neutral singlet iron catalyst 1Fe(CO)4 activates all three C-X bonds via barriers that are lower than those for Pd(PH3)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, 1Fe(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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DO - 10.1039/c8cp07671e

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JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

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ER -

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

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