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Spin polarization assisted facile C-H activation by an S = 1 iron(iv)-bisimido complex: a comprehensive spectroscopic and theoretical investigation.

ABSTRACT: High valent iron terminal imido species (Fe[double bond, length as m-dash]NR) have been shown to be key reactive intermediates in C-H functionalization. However, the detailed structure-reactivity relationship in Fe[double bond, length as m-dash]NR species derived from studies of structurally well-characterized high-valent Fe[double bond, length as m-dash]NR complexes are still scarce, and the impact of imido N-substituents (electron-donating vs. electron-withdrawing) on their electronic structures and reactivities has not been thoroughly explored. In this study, we report spectroscopic and computational studies on a rare S = 1 iron(iv)-bisimido complex featuring trifluoromethyl groups on the imido N-substituents, [(IPr)Fe(NC(CF₃)₂Ph)₂] (2), and two closely related S = 0 congeners bearing alkyl and aryl substituents, [(IPr)Fe(NC(CMe₃)₂Ph)₂] (3) and [(IPr)Fe(NDipp)₂] (1), respectively. Compared with 1 and 3, 2 exhibits a decreased Fe[double bond, length as m-dash]NR bond covalency due to the electron-withdrawing and the steric effect of the N-substituents, which further leads to a pseudo doubly degenerate ground electronic structure and spin polarization induced β spin density on the imido nitrogens. This unique electronic structure, which differs from those of the well-studied Fe(iv)-oxido complexes and many previously reported Fe(iv)-imido complexes, provides both kinetic and thermodynamic advantages for facile C-H activation, compared to the S = 0 counterparts.

SUBMITTER: Xiong J

PROVIDER: S-EPMC10016330 | biostudies-literature | 2023 Mar

REPOSITORIES: biostudies-literature

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Spin polarization assisted facile C-H activation by an <i>S</i> = 1 iron(iv)-bisimido complex: a comprehensive spectroscopic and theoretical investigation.

Xiong Jin J Liu Qing Q Lavina Barbara B Hu Michael Y MY Zhao Jiyong J Alp Esen E EE Deng Liang L Ye Shengfa S Guo Yisong Y

Chemical science 20230215 11

High valent iron terminal imido species (Fe[double bond, length as m-dash]NR) have been shown to be key reactive intermediates in C-H functionalization. However, the detailed structure-reactivity relationship in Fe[double bond, length as m-dash]NR species derived from studies of structurally well-characterized high-valent Fe[double bond, length as m-dash]NR complexes are still scarce, and the impact of imido N-substituents (electron-donating <i>vs.</i> electron-withdrawing) on their electronic s ...[more]

PMID: 36937578

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Project description:Six-coordinate MnIII complexes are typically high-spin (S = 2), however, the scorpionate ligand, both in its traditional, hydridotris(pyrazolyl)borate form, Tp- and Tp*- (the latter with 3,5-dimethylpyrazole substituents) and in an aryltris(carbene)borate (i.e., N-heterocyclic carbene, NHC) form, [Ph(MeIm)3B]-, (MeIm = 3-methylimidazole) lead to formation of bis(scorpionate) complexes of MnIII with spin triplet ground states; three of which were investigated herein: [Tp2Mn]SbF6 (1SBF6), [Tp*2Mn]SbF6 (2SBF6), and [{Ph(MeIm)3B}2Mn]CF3SO3 (3CF3SO3). These trigonally symmetric complexes were studied experimentally by magnetic circular dichroism (MCD) spectroscopy (the propensity of 3 to oxidize to MnIV precluded collection of useful MCD data) including variable temperatures and fields (VTVH-MCD) and computationally by ab initio CASSCF/NEVPT2 methods. These combined experimental and theoretical techniques establish the 3A2g electronic ground state for the three complexes, and provide information on the energy of the "conventional" high-spin excited state (5Eg) and other, triplet excited states. These results show the electronic effect of pyrazole ring substituents in comparing 1 and 2. The tunability of the scorpionate ligand, even by perhaps the simplest change (from pyrazole in 1 to 3,5-dimethylpyrazole in 2) is quantitatively manifested through perturbations in ligand-field excited-state energies that impact ground-state zero-field splittings. The comparison with the NHC donor is much more dramatic. In 3, the stronger σ-donor properties of the NHC lead to a quantitatively different electronic structure, so that the lowest lying spin triplet excited state, 3Eg, is much closer in energy to the ground state than in 1 or 2. The zero-field splitting (zfs) parameters of the three complexes were calculated and in the case of 1 and 2 compare closely to experiment (lower by < 10%, < 2 cm-1 in absolute terms); for 3 the large magnitude zfs is reproduced, although there is ambiguity about its sign. The comprehensive picture obtained for these bis(scorpionate) MnIII complexes provides quantitative insight into the role played by the scorpionate ligand in stabilizing unusual electronic structures.

Dataset Information

Spin polarization assisted facile C-H activation by an S = 1 iron(iv)-bisimido complex: a comprehensive spectroscopic and theoretical investigation.

Publications

Spin polarization assisted facile C-H activation by an <i>S</i> = 1 iron(iv)-bisimido complex: a comprehensive spectroscopic and theoretical investigation.

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