TY - JOUR
T1 - Theoretical investigation on the elusive structure-activity relationship of bioinspired high-valence nickel-halogen complexes in oxidative fluorination reactions
AU - Zhou, Anran
AU - Li, Xiao Xi
AU - Sun, Dongru
AU - Cao, Xuanyu
AU - Wu, Zhimin
AU - Chen, Huanhuan
AU - Zhao, Yufen
AU - Nam, Wonwoo
AU - Wang, Yong
N1 - Publisher Copyright:
© 2023 The Royal Society of Chemistry.
PY - 2023/1/10
Y1 - 2023/1/10
N2 - Very recently, bioinspired high-valence metal-halogen complexes have been proven to be competent oxidants in the C-H bond activation and heteroatom dihalogenation reactions. However, the structure-activity relationship of such active species and the reaction mechanisms of oxidations mediated by these oxidants are still elusive. In this study, density functional theory (DFT) calculations were performed to systematically study the oxidizing ability of the high-valence NiIII-X (X = F and Cl) complexes Et4N[NiIII(Cl/F)(L)], (1Cl/F, Et = ethyl, L = N,N‘-(2,6-dimethylphenyl)-2,6-pyridinedicarboxamide), such as the reaction mechanism of fluorination of 1,4-cyclohexadiene (CHD) by 1F in the presence of AgF and the reaction mechanism of difluorination of triphenyl phosphine (PPh3) by 1F. All calculated results fit well with the experiments and present new mechanistic findings. The C-H bond activation by the high-valence nickel(iii)-halogen complexes was found to proceed via a hydrogen-atom transfer (HAT) mechanism by analysis of the molecular orbitals of the transition states. C-H bond activation by 1F takes a Ni-F-H angle of ca. 180°, whereas that by 1Cl takes an angle of ca. 120° on the transition states. These results indicate that the exchange-enhanced reactivity is responsible for the dramatic oxidative difference between these two oxidants. The role of AgF in C-H fluorination of CHD by 1F is proposed to act as a Lewis acid adduct, AgF-binding Ni(iii)-fluorine complex 1F-Ag-F, which acts both as an oxidant in C-H bond activation and as a fluorine donor in the fluorination step. A cooperative oxidation mechanism involving two 1F oxidants was proposed for the difluorination of PPh3 by 1F. These theoretical findings will enrich the knowledge of high-valence metal-halogen chemistry and play a positive role in the rational design of new catalysts.
AB - Very recently, bioinspired high-valence metal-halogen complexes have been proven to be competent oxidants in the C-H bond activation and heteroatom dihalogenation reactions. However, the structure-activity relationship of such active species and the reaction mechanisms of oxidations mediated by these oxidants are still elusive. In this study, density functional theory (DFT) calculations were performed to systematically study the oxidizing ability of the high-valence NiIII-X (X = F and Cl) complexes Et4N[NiIII(Cl/F)(L)], (1Cl/F, Et = ethyl, L = N,N‘-(2,6-dimethylphenyl)-2,6-pyridinedicarboxamide), such as the reaction mechanism of fluorination of 1,4-cyclohexadiene (CHD) by 1F in the presence of AgF and the reaction mechanism of difluorination of triphenyl phosphine (PPh3) by 1F. All calculated results fit well with the experiments and present new mechanistic findings. The C-H bond activation by the high-valence nickel(iii)-halogen complexes was found to proceed via a hydrogen-atom transfer (HAT) mechanism by analysis of the molecular orbitals of the transition states. C-H bond activation by 1F takes a Ni-F-H angle of ca. 180°, whereas that by 1Cl takes an angle of ca. 120° on the transition states. These results indicate that the exchange-enhanced reactivity is responsible for the dramatic oxidative difference between these two oxidants. The role of AgF in C-H fluorination of CHD by 1F is proposed to act as a Lewis acid adduct, AgF-binding Ni(iii)-fluorine complex 1F-Ag-F, which acts both as an oxidant in C-H bond activation and as a fluorine donor in the fluorination step. A cooperative oxidation mechanism involving two 1F oxidants was proposed for the difluorination of PPh3 by 1F. These theoretical findings will enrich the knowledge of high-valence metal-halogen chemistry and play a positive role in the rational design of new catalysts.
UR - http://www.scopus.com/inward/record.url?scp=85147164536&partnerID=8YFLogxK
U2 - 10.1039/d2dt03212k
DO - 10.1039/d2dt03212k
M3 - Article
C2 - 36691931
AN - SCOPUS:85147164536
SN - 1477-9226
VL - 52
SP - 1977
EP - 1988
JO - Dalton Transactions
JF - Dalton Transactions
IS - 7
ER -