Theoretical studies unveil the unusual bonding in oxygenation reactions involving cobalt(<scp>ii</scp>)-iodylarene complexes

Chen, Xiaolu; Sun, Dongru; Gao, Lanping; Zhao, Yufen; Visser, Sam P. de; Wang, Yong

doi:10.1039/d0cc07894h

Cited by 4 publications

(2 citation statements)

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“…Activation energies for the conversion of 1 LBHB and 1′ LBHB to 2 are as large as 26.2 and 26.0 kcal mol –1 , and the endothermicities are 23.6 and 24.7 kcal mol –1 , respectively. The conversion of the cobalt–iodosylarene species 1 LBHB and 1′ LBHB to the cobalt–oxyl species 2 is not feasible both kinetically and thermodynamically, like some other metal–iodosylarene/iodylarene complexes. − Thus, due to the oxo-wall proposed by Gray and co-workers, ,− only 1 LBHB and 1′ LBHB are left as the potential oxidants for styrene oxidation by 1 in the presence of HOTf.…”

Section: Results and Discussionmentioning

confidence: 99%

Brønsted Acids Promote Olefin Oxidations by Bioinspired Nonheme Co^III(PhIO)(OH) Complexes: A Role for Low-Barrier Hydrogen Bonds

et al. 2023

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Introduction of Brønsted acids into biomimetic nonheme reactions promotes the oxidative ability of metal−oxygen complexes significantly. However, the molecular machinery of the promoted effects is missing. Herein, a comprehensive investigation of styrene oxidation by a cobalt(III)−iodosylbenzene complex, [(TQA)-Co III (OIPh)(OH)] 2+ (1, TQA = tris(2-quinolylmethyl)amine), in the presence and absence of triflic acid (HOTf) was performed using density functional theory calculations. Results revealed for the first time that there is a low-barrier hydrogen bond (LBHB) between HOTf and the hydroxyl ligand of 1, which forms two valenceresonance structures [(TQA)Co III (OIPh)(HO − --HOTf)] 2+ (1 LBHB ) and [(TQA)Co III (OIPh)(H 2 O--OTf − )] 2+ (1′ LBHB ). Due to the oxo-wall, these complexes (1 LBHB and 1′ LBHB ) cannot convert to high-valent cobalt−oxyl species. Instead, styrene oxidation by these oxidants (1 LBHB and 1′ LBHB ) shows novel spin-state selectivity, i.e., on the ground closed-shell singlet state, styrene is oxidized to an epoxide, whereas on the excited triplet and quintet states, an aldehyde product, phenylacetaldehyde, is formed. The preferred pathway is styrene oxidation by 1′ LBHB , which is initiated by a rate-limiting bond-formation-coupled electron transfer process with an energy barrier of 12.2 kcal mol −1 . The nascent PhIO-styrene-radical-cation intermediate undergoes an intramolecular rearrangement to produce an aldehyde. The halogen bond between the OH − /H 2 O ligand and the iodine of PhIO modulates the activity of the cobalt−iodosylarene complexes 1 LBHB and 1′ LBHB . These new mechanistic findings enrich our knowledge of nonheme chemistry and hypervalent iodine chemistry and will play a positive role in the rational design of new catalysts.

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Section: Results and Discussionmentioning

confidence: 99%

Brønsted Acids Promote Olefin Oxidations by Bioinspired Nonheme Co^III(PhIO)(OH) Complexes: A Role for Low-Barrier Hydrogen Bonds

et al. 2023

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“…The employed method has been extensively used in non-heme chemistry and has been proven to be reliable. [51][52][53][54][55][56][57][58][59][60][61][62] All computational details are presented in the ESI. †…”

Section: Computational Methodologymentioning

confidence: 99%

The elusive reaction mechanism of Mn(ii)-mediated benzylic oxidation of alkylarene by H₂O₂: a gem-diol mechanism or a dual hydrogen abstraction mechanism?

Wang,

Sun,

et al. 2023

Dalton Trans.

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Theoretical investigation on the elusive biomimetic iron(III)-iodosylarene chemistry: An unusual hydride transfer triggers the Ritter reaction

Gao

Chen

Sun

et al. 2021

Chinese Chemical Letters

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Theoretical studies unveil the unusual bonding in oxygenation reactions involving cobalt(ii)-iodylarene complexes

Abstract: DFT calculations reveal that the iodine of cobalt(II)-iodylarene complexes acts as a directing group via halogen bonding interaction to substrates. A transient 3c-4e bond is formed during oxidation reactions to...

Cited by 4 publications

References 27 publications

Brønsted Acids Promote Olefin Oxidations by Bioinspired Nonheme Co^III(PhIO)(OH) Complexes: A Role for Low-Barrier Hydrogen Bonds

Brønsted Acids Promote Olefin Oxidations by Bioinspired Nonheme Co^III(PhIO)(OH) Complexes: A Role for Low-Barrier Hydrogen Bonds

The elusive reaction mechanism of Mn(ii)-mediated benzylic oxidation of alkylarene by H₂O₂: a gem-diol mechanism or a dual hydrogen abstraction mechanism?

Theoretical investigation on the elusive biomimetic iron(III)-iodosylarene chemistry: An unusual hydride transfer triggers the Ritter reaction

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Theoretical studies unveil the unusual bonding in oxygenation reactions involving cobalt(ii)-iodylarene complexes

Abstract: DFT calculations reveal that the iodine of cobalt(II)-iodylarene complexes acts as a directing group via halogen bonding interaction to substrates. A transient 3c-4e bond is formed during oxidation reactions to...

Cited by 4 publications

References 27 publications

Brønsted Acids Promote Olefin Oxidations by Bioinspired Nonheme CoIII(PhIO)(OH) Complexes: A Role for Low-Barrier Hydrogen Bonds

Brønsted Acids Promote Olefin Oxidations by Bioinspired Nonheme CoIII(PhIO)(OH) Complexes: A Role for Low-Barrier Hydrogen Bonds

The elusive reaction mechanism of Mn(ii)-mediated benzylic oxidation of alkylarene by H2O2: a gem-diol mechanism or a dual hydrogen abstraction mechanism?

Theoretical investigation on the elusive biomimetic iron(III)-iodosylarene chemistry: An unusual hydride transfer triggers the Ritter reaction

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Brønsted Acids Promote Olefin Oxidations by Bioinspired Nonheme Co^III(PhIO)(OH) Complexes: A Role for Low-Barrier Hydrogen Bonds

Brønsted Acids Promote Olefin Oxidations by Bioinspired Nonheme Co^III(PhIO)(OH) Complexes: A Role for Low-Barrier Hydrogen Bonds

The elusive reaction mechanism of Mn(ii)-mediated benzylic oxidation of alkylarene by H₂O₂: a gem-diol mechanism or a dual hydrogen abstraction mechanism?