TY - JOUR
T1 - Iron-Catalyzed Activation of Carbon-Halogen Bonds
AU - Tiekink, Eveline H.
AU - Poets, Henrik
AU - Hamlin, Trevor A.
AU - Bickelhaupt, F. Matthias
N1 - Publisher Copyright:
© 2024 The Authors. Published by American Chemical Society.
PY - 2025/1/13
Y1 - 2025/1/13
N2 - We have studied the cross-coupling reaction of C(spn)-X bonds (n = 1-3; X = F, Cl, Br, I) mediated by the model iron-d8 catalyst Fe(CO)4 with the archetypal model substrates H3C-CH2-X, H2C═CH-X, and HC≡C-X, utilizing relativistic density functional theory at ZORA-OPBE/TZ2P. The barrier of the oxidative-addition step decreases as the C(spn)-X bond varies from X = F to Cl to Br to I and from C(sp3) to C(sp2) to C(sp). Activation strain and energy decomposition analyses uncover that the lowering of the reaction barrier from X = F to I is caused by (i) a weaker C(spn)-X bond that needs to be broken, (ii) enhanced HOMO-LUMO interactions, and (iii) a stronger electrostatic attraction between the catalyst and the substrate due to the more diffuse electron density and higher nuclear charge of the X atom when varying from X = F to I.
AB - We have studied the cross-coupling reaction of C(spn)-X bonds (n = 1-3; X = F, Cl, Br, I) mediated by the model iron-d8 catalyst Fe(CO)4 with the archetypal model substrates H3C-CH2-X, H2C═CH-X, and HC≡C-X, utilizing relativistic density functional theory at ZORA-OPBE/TZ2P. The barrier of the oxidative-addition step decreases as the C(spn)-X bond varies from X = F to Cl to Br to I and from C(sp3) to C(sp2) to C(sp). Activation strain and energy decomposition analyses uncover that the lowering of the reaction barrier from X = F to I is caused by (i) a weaker C(spn)-X bond that needs to be broken, (ii) enhanced HOMO-LUMO interactions, and (iii) a stronger electrostatic attraction between the catalyst and the substrate due to the more diffuse electron density and higher nuclear charge of the X atom when varying from X = F to I.
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U2 - 10.1021/acs.organomet.4c00343
DO - 10.1021/acs.organomet.4c00343
M3 - Article
AN - SCOPUS:85207810365
SN - 0276-7333
VL - 44
SP - 36
EP - 45
JO - Organometallics
JF - Organometallics
IS - 1
ER -