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DFT Mechanistic Insights into Aldehyde Deformylations with Biomimetic Metal-Dioxygen Complexes: Distinct Mechanisms and Reaction Rules.

ABSTRACT: Aldehyde deformylations occurring in organisms are catalyzed by metalloenzymes through metal-dioxygen active cores, attracting great interest to study small-molecule metal-dioxygen complexes for understanding relevant biological processes and developing biomimetic catalysts for aerobic transformations. As the known deformylation mechanisms, including nucleophilic attack, aldehyde α-H-atom abstraction, and aldehyde hydrogen atom abstraction, undergo outer-sphere pathways, we herein report a distinct inner-sphere mechanism based on density functional theory (DFT) mechanistic studies of aldehyde deformylations with a copper (II)-superoxo complex. The inner-sphere mechanism proceeds via a sequence mainly including aldehyde end-on coordination, homolytic aldehyde C-C bond cleavage, and dioxygen O-O bond cleavage, among which the C-C bond cleavage is the rate-determining step with a barrier substantially lower than those of outer-sphere pathways. The aldehyde C-C bond cleavage, enabled through the activation of the dioxygen ligand radical in a second-order nucleophilic substitution (S_N2)-like fashion, leads to an alkyl radical and facilitates the subsequent dioxygen O-O bond cleavage. Furthermore, we deduced the rules for the reactions of metal-dioxygen complexes with aldehydes and nitriles via the inner-sphere mechanism. Expectedly, our proposed inner-sphere mechanisms and the reaction rules offer another perspective to understand relevant biological processes involving metal-dioxygen cores and to discover metal-dioxygen catalysts for aerobic transformations.

SUBMITTER: Zhao R

PROVIDER: S-EPMC8970012 | biostudies-literature | 2022 Mar

REPOSITORIES: biostudies-literature

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DFT Mechanistic Insights into Aldehyde Deformylations with Biomimetic Metal-Dioxygen Complexes: Distinct Mechanisms and Reaction Rules.

Zhao Ruihua R Zhang Bei-Bei BB Liu Zheyuan Z Cheng Gui-Juan GJ Wang Zhi-Xiang ZX

JACS Au 20220225 3

Aldehyde deformylations occurring in organisms are catalyzed by metalloenzymes through metal-dioxygen active cores, attracting great interest to study small-molecule metal-dioxygen complexes for understanding relevant biological processes and developing biomimetic catalysts for aerobic transformations. As the known deformylation mechanisms, including nucleophilic attack, aldehyde α-H-atom abstraction, and aldehyde hydrogen atom abstraction, undergo outer-sphere pathways, we herein report a disti ...[more]

PMID: 35373207

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Project description:This study describes the O2 reactivity of a series of high-spin mononuclear Fe(II) complexes each containing the facially coordinating tris(4,5-diphenyl-1-methylimidazol-2-yl)phosphine ((Ph2)TIP) ligand and one of the following bidentate, redox-active ligands: 4-tert-butylcatecholate ((tBu)CatH(-)), 4,6-di-tert-butyl-2-aminophenolate ((tBu2)APH(-)), or 4-tert-butyl-1,2-phenylenediamine ((tBu)PDA). The preparation and X-ray structural characterization of [Fe(2+)((Ph2)TIP)((tBu)CatH)]OTf, [3]OTf and [Fe(2+)((Ph2)TIP)((tBu)PDA)](OTf)2, [4](OTf)2 are described here, whereas [Fe(2+)((Ph2)TIP)((tBu2)APH)]OTf, [2]OTf was reported in our previous paper [Bittner et al., Chem.-Eur. J. 2013, 19, 9686-9698]. These complexes mimic the substrate-bound active sites of nonheme iron dioxygenases, which catalyze the oxidative ring-cleavage of aromatic substrates like catechols and aminophenols. Each complex is oxidized in the presence of O2, and the geometric and electronic structures of the resulting complexes were examined with spectroscopic (absorption, EPR, Mössbauer, resonance Raman) and density functional theory (DFT) methods. Complex [3]OTf reacts rapidly with O2 to yield the ferric-catecholate species [Fe(3+)((Ph2)TIP)((tBu)Cat)](+) (3(ox)), which undergoes further oxidation to generate an extradiol cleavage product. In contrast, complex [4](2+) experiences a two-electron (2e(-)), ligand-based oxidation to give [Fe(2+)((Ph2)TIP)((tBu)DIBQ)](2+) (4(ox)), where DIBQ is o-diiminobenzoquinone. The reaction of [2](+) with O2 is also a 2e(-) process, yet in this case both the Fe center and (tBu2)AP ligand are oxidized; the resulting complex (2(ox)) is best described as [Fe(3+)((Ph2)TIP)((tBu2)ISQ)](+), where ISQ is o-iminobenzosemiquinone. Thus, the oxidized complexes display a remarkable continuum of electronic structures ranging from [Fe(3+)(L(2-))](+) (3(ox)) to [Fe(3+)(L(•-))](2+) (2(ox)) to [Fe(2+)(L(0))](2+) (4(ox)). Notably, the O2 reaction rates vary by a factor of 10(5) across the series, following the order [3](+) > [2](+) > [4](2+), even though the complexes have similar structures and Fe(3+/2+) redox potentials. To account for the kinetic data, we examined the relative abilities of the title complexes to bind O2 and participate in H-atom transfer reactions. We conclude that the trend in O2 reactivity can be rationalized by accounting for the role of proton transfer(s) in the overall reaction.

Dataset Information

DFT Mechanistic Insights into Aldehyde Deformylations with Biomimetic Metal-Dioxygen Complexes: Distinct Mechanisms and Reaction Rules.

Publications

DFT Mechanistic Insights into Aldehyde Deformylations with Biomimetic Metal-Dioxygen Complexes: Distinct Mechanisms and Reaction Rules.

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