Computational I(III)—X BDEs for Benziodoxol(on)e‐based Hypervalent Iodine Reagents: Implications for Their Functional Group Transfer Abilities

Yang, Jin‐Dong; Li, Man; Xue, Xiao‐Song

doi:10.1002/cjoc.201800549

Cited by 30 publications

(28 citation statements)

References 64 publications

(5 reference statements)

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“…It is remarkable that despite the higher IÀ CN bond dissociation energy compared to IÀ N 3 bond in ABX, these reactions have a similar outcome. [13] The 1-electron process reported for iron herein differs also with the 2-electron oxidative processes reported for the reaction of a variety of λ 3 -iodanes with 4d and 5d transition metal complexes (Pd, Rh, Ir, Au), [14] as well as with late 3d transition metals, such as Cu and Ni. [15] The N 3 N' ligand stabilizes the electrophilic Fe IV cyanide complex, [(N 3 N')Fe IV (CN)] ( 4) as reported by the Schrock group.…”

Section: Resultsmentioning

confidence: 46%

Synthesis of Fe^III and Fe^IV Cyanide Complexes Using Hypervalent Iodine Reagents as Cyano‐Transfer One‐Electron Oxidants

et al. 2022

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We disclose a new reactivity mode for electrophilic cyano λ 3 -iodanes as group transfer one-electron oxidants to synthesize Fe III and Fe IV cyanide complexes. The inherent thermal instability of high-valent Fe IV compounds without π-donor ligands (such as oxido (O 2À ), imido (RN 2À ) or nitrido (N 3À )) makes their isolation and structural characterization a very challenging task. We report the synthesis of an Fe IV cyanide complex [(N 3 N')FeCN] (4) by two consecutive single electron transfer (SET) processes from Fe II precursor [(N 3 N')FeLi(THF)] (1) with cyanobenziodoxolone (CBX). The Fe IV complex can also be prepared by reaction of [(N 3 N')Fe III ] (3) with CBX. In contrast, the oxidation of Fe II with 1-cyano-3,3-dimethyl-3-(1H)-1,2benziodoxole (CDBX) enables the preparation of Fe III cyanide complex [(N 3 N')Fe III (CN)(Li)(THF) 3 ] (2-Li THF ). Complexes 4 and 2-Li THF have been structurally characterized by single crystal X-ray diffraction and their electronic structure has been examined by Mössbauer, EPR spectroscopy, and computational analyses.

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Section: Resultsmentioning

confidence: 46%

Synthesis of Fe^III and Fe^IV Cyanide Complexes Using Hypervalent Iodine Reagents as Cyano‐Transfer One‐Electron Oxidants

et al. 2022

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“…Xue and Yang and co‐workers studied the bond dissociation energy (BDE) of the exocyclic ligand of benziodoxol(on)e‐based hypervalent iodine reagents using DFT [109] . They found that meta and para substituents had a small influence on the BDE, while ortho substituents could significantly decrease the BDE by means of steric hindrance.…”

Section: Computational Insightsmentioning

confidence: 99%

Cyclic Haloiodanes: Syntheses, Applications and Fundamental Studies

Robidas

Legault

2021

Helvetica Chimica Acta

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Hypervalent iodine reagents are powerful tools in contemporary organic synthesis. They have found numerous applications in modern oxidative transformations. The unique reactivity of hypervalent iodine allows access to unconventional electrophilic synthons. For example, electrophilic halogenation chemistry has been greatly expanded by the study of various haloiodanes. Cyclic λ3‐haloiodanes are versatile reagents which can promote reactions such as halogenations, halocyclizations and oxidations. Their peculiar reactivity sets them apart from traditional sources of electrophilic halogens. Furthermore, they offer a broad range of reactivities which have been exploited in more diversified transformations. This review summarizes the different syntheses and derivatives of these cyclic haloiodanes, their applications and mechanistic insights as well as the relevant computational, structural and kinetic studies.

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“…Heterolytic or homolytic cleavage of a weak, threecenter four-electron (3c-4e) bond of HVI progresses the chemical reaction. Therefore, the BDE of the 3c-4e bond of HVI is an essential parameter that has been calculated by the DFT method on demand [16][17][18][19] . We previously reported the BDE value of 3c-4e bonds in various HVIs on the basis of DFT calculations 19 .…”

Section: Machine Learning Enabling Prediction Of the Bond Dissociation Enthalpy Of Hypervalent Iodine From Smilesmentioning

confidence: 99%

Machine learning enabling prediction of the bond dissociation enthalpy of hypervalent iodine from SMILES

Nakajima

Nemoto

2021

Sci Rep

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Machine learning to create models on the basis of big data enables predictions from new input data. Many tasks formerly performed by humans can now be achieved by machine learning algorithms in various fields, including scientific areas. Hypervalent iodine compounds (HVIs) have long been applied as useful reactive molecules. The bond dissociation enthalpy (BDE) value is an important indicator of reactivity and stability. Experimentally measuring the BDE value of HVIs is difficult, however, and the value has been estimated by quantum calculations, especially density functional theory (DFT) calculations. Although DFT calculations can access the BDE value with high accuracy, the process is highly time-consuming. Thus, we aimed to reduce the time for predicting the BDE by applying machine learning. We calculated the BDE of more than 1000 HVIs using DFT calculations, and performed machine learning. Converting SMILES strings to Avalon fingerprints and learning using a traditional Elastic Net made it possible to predict the BDE value with high accuracy. Furthermore, an applicability domain search revealed that the learning model could accurately predict the BDE even for uncovered inputs that were not completely included in the training data.

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Computational I(III)—X BDEs for Benziodoxol(on)e‐based Hypervalent Iodine Reagents: Implications for Their Functional Group Transfer Abilities

Cited by 30 publications

References 64 publications

Synthesis of Fe^III and Fe^IV Cyanide Complexes Using Hypervalent Iodine Reagents as Cyano‐Transfer One‐Electron Oxidants

Synthesis of Fe^III and Fe^IV Cyanide Complexes Using Hypervalent Iodine Reagents as Cyano‐Transfer One‐Electron Oxidants

Cyclic Haloiodanes: Syntheses, Applications and Fundamental Studies

Machine learning enabling prediction of the bond dissociation enthalpy of hypervalent iodine from SMILES

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Computational I(III)—X BDEs for Benziodoxol(on)e‐based Hypervalent Iodine Reagents: Implications for Their Functional Group Transfer Abilities

Cited by 30 publications

References 64 publications

Synthesis of FeIII and FeIV Cyanide Complexes Using Hypervalent Iodine Reagents as Cyano‐Transfer One‐Electron Oxidants

Synthesis of FeIII and FeIV Cyanide Complexes Using Hypervalent Iodine Reagents as Cyano‐Transfer One‐Electron Oxidants

Cyclic Haloiodanes: Syntheses, Applications and Fundamental Studies

Machine learning enabling prediction of the bond dissociation enthalpy of hypervalent iodine from SMILES

Contact Info

Product

Resources

About

Synthesis of Fe^III and Fe^IV Cyanide Complexes Using Hypervalent Iodine Reagents as Cyano‐Transfer One‐Electron Oxidants

Synthesis of Fe^III and Fe^IV Cyanide Complexes Using Hypervalent Iodine Reagents as Cyano‐Transfer One‐Electron Oxidants