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Sulfonyl Nitrene and Amidyl Radical: Structure and Reactivity.

ABSTRACT: Photocatalytic generation of nitrenes and radicals can be used to tune or even control their reactivity. Photocatalytic activation of sulfonyl azides leads to the elimination of N₂ and the resulting reactive species initiate C-H activations and amide formation reactions. Here, we present reactive radicals that are generated from sulfonyl azides: sulfonyl nitrene radical anion, sulfonyl nitrene and sulfonyl amidyl radical, and test their gas phase reactivity in C-H activation reactions. The sulfonyl nitrene radical anion is the least reactive and its reactivity is governed by the proton coupled electron transfer mechanism. In contrast, sulfonyl nitrene and sulfonyl amidyl radicals react via hydrogen atom transfer pathways. These reactivities and detailed characterization of the radicals with vibrational spectroscopy and with DFT calculations provide information necessary for taking control over the reactivity of these intermediates.

SUBMITTER: Zelenka J

PROVIDER: S-EPMC9323475 | biostudies-literature | 2022 May

REPOSITORIES: biostudies-literature

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Sulfonyl Nitrene and Amidyl Radical: Structure and Reactivity.

Zelenka Jan J Pereverzev Aleksandr A Jahn Ullrich U Roithová Jana J

Chemistry (Weinheim an der Bergstrasse, Germany) 20220405 28

Photocatalytic generation of nitrenes and radicals can be used to tune or even control their reactivity. Photocatalytic activation of sulfonyl azides leads to the elimination of N<sub>2</sub> and the resulting reactive species initiate C-H activations and amide formation reactions. Here, we present reactive radicals that are generated from sulfonyl azides: sulfonyl nitrene radical anion, sulfonyl nitrene and sulfonyl amidyl radical, and test their gas phase reactivity in C-H activation reactions ...[more]

PMID: 35266598

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Project description:To fully characterize the Co(III)-'nitrene radical' species that are proposed as intermediates in nitrene transfer reactions mediated by cobalt(II) porphyrins, different combinations of cobalt(II) complexes of porphyrins and nitrene transfer reagents were combined, and the generated species were studied using EPR, UV-vis, IR, VCD, UHR-ESI-MS, and XANES/XAFS measurements. Reactions of cobalt(II) porphyrins 1(P1) (P1 = meso-tetraphenylporphyrin (TPP)) and 1(P2) (P2 = 3,5-Di(t)Bu-ChenPhyrin) with organic azides 2(Ns) (NsN3), 2(Ts) (TsN3), and 2(Troc) (TrocN3) led to the formation of mono-nitrene species 3(P1)(Ns), 3(P2)(Ts), and 3(P2)(Troc), respectively, which are best described as [Co(III)(por)(NR″(•-))] nitrene radicals (imidyl radicals) resulting from single electron transfer from the cobalt(II) porphyrin to the 'nitrene' moiety (Ns: R″ = -SO2-p-C6H5NO2; Ts: R″ = -SO2C6H6; Troc: R″ = -C(O)OCH2CCl3). Remarkably, the reaction of 1(P1) with N-nosyl iminoiodane (PhI═NNs) 4(Ns) led to the formation of a bis-nitrene species 5(P1)(Ns). This species is best described as a triple-radical complex [(por(•-))Co(III)(NR″(•-))2] containing three ligand-centered unpaired electrons: two nitrene radicals (NR″(•-)) and one oxidized porphyrin radical (por(•-)). Thus, the formation of the second nitrene radical involves another intramolecular one-electron transfer to the "nitrene" moiety, but now from the porphyrin ring instead of the metal center. Interestingly, this bis-nitrene species is observed only on reacting 4(Ns) with 1(P1). Reaction of the more bulky 1(P2) with 4(Ns) results again in formation of mainly mono-nitrene species 3(P2)(Ns) according to EPR and ESI-MS spectroscopic studies. The mono- and bis-nitrene species were initially expected to be five- and six-coordinate species, respectively, but XANES data revealed that both mono- and bis-nitrene species are six-coordinate O(h) species. The nature of the sixth ligand bound to cobalt(III) in the mono-nitrene case remains elusive, but some plausible candidates are NH3, NH2(-), NsNH(-), and OH(-); NsNH(-) being the most plausible. Conversion of mono-nitrene species 3(P1)(Ns) into bis-nitrene species 5(P1)(Ns) upon reaction with 4(Ns) was demonstrated. Solutions containing 3(P1)(Ns) and 5(P1)(Ns) proved to be still active in catalytic aziridination of styrene, consistent with their proposed key involvement in nitrene transfer reactions mediated by cobalt(II) porphyrins.

Project description:Detailed electronic structure and its correlation with the intramolecular C-H amination reactivity of Fe-porphyrin-nitrene intermediates bearing different "axial" coordination have been investigated using multiconfigurational complete active space self-consistent field (CASSCF), N-electron valence perturbation theory (NEVPT2), and hybrid density functional theory (DFT-B3LYP) calculations. Three types of "axial" coordination, -OMe/-O(H)Me (1-Sul/2-Sul), -SMe/-S(H)Me (3-Sul/4-Sul), and -NMeIm (MeIm = 3-methyl-imidazole) (5-Sul) mimicking serine, cysteine, and histidine, respectively, along with no axial coordination (6-Sul) have been considered to decipher how the "axial" coordination of different strengths regulates the electronic integrity of the Fe-N core and nitrene-transfer reactivity of Fe-porphyrin-nitrene intermediates. CASSCF-based natural orbitals reveal two distinct classes of electronic structures: Fe-nitrenes (1-Sul and 3-Sul) with relatively stronger axial coordination (-OMe and -SMe) display "imidyl" nature and those (2-Sul, 4-Sul, and 6-Sul) with weaker axial coordination (-O(H)Me, -S(H)Me and no axial coordination) exhibit "imido-like" character. A borderline between the two classes is also observed with NMeIm axial coordination (5-Sul). Axial coordination of different strengths not only regulates the electronic structure but also modulates the Fe-3d orbital energies, as revealed through the d-d transition energies obtained by CASSCF/NEVPT2 calculations. The relatively lower energy of Fe-3dz2 orbital allows easy access to low-lying high-spin quintet states in the cases of weaker "axial" coordination (2-Sul, 4-Sul, and 6-Sul), and the associated hydrogen atom transfer (HAT) reactivity appears to involve two-state triplet-quintet reactivity through minimum energy crossing point (3,5MECP) between the spin states. In stark contrast, Fe-nitrenes with relatively stronger "axial" coordination (1-Sul and 3-Sul) undergo triplet-only HAT reactivity. Overall, this in-depth electronic structure investigation and HAT reactivity evaluation reveal that the weaker axial coordination in Fe-porphyrin-nitrene complexes (2-Sul, 4-Sul, and 6-Sul) can promote more efficient C-H oxidation through the quintet spin state.

Dataset Information

Sulfonyl Nitrene and Amidyl Radical: Structure and Reactivity.

Publications

Sulfonyl Nitrene and Amidyl Radical: Structure and Reactivity.

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