The Mechanism of E–H (E = N, O) Bond Activation by a Germanium Corrole Complex: A Combined Experimental and Computational Study

Fang, Hanming; Jing, Huize; Ge, Haonan; Brothers, Penelope J.; Fu, Xuefeng; Ye, Shengfa

doi:10.1021/jacs.5b01121

Cited by 30 publications

(29 citation statements)

References 66 publications

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“…In contrast to the [(TPFC)Ge] + cation, the vacant orbitals on these cationic centers were the two pure p orbitals (schematic representation of 1-coordinate E(II) cation in Figure c). , This work presents a rare example of group 14 cations with vacant sp-hybridized orbitals illustrating its distinctive reactivity. Similarly, our previous studies , showed that the unpaired electron in the [(TPFC)Ge] 0 radical was mainly localized in a sp-hybridized orbital on the germanium center rather than in a pure p orbital as is typical of the traditional heavier group 14 radicals. , …”

Section: Resultssupporting

confidence: 62%

“…4,27 This work presents a rare example of group 14 cations with vacant sphybridized orbitals illustrating its distinctive reactivity. Similarly, our previous studies 36,62 showed that the unpaired electron in the [(TPFC)Ge] 0 radical was mainly localized in a sphybridized orbital on the germanium center rather than in a pure p orbital as is typical of the traditional heavier group 14 radicals. 63,64 ■ CONCLUSIONS A square planar, tetra-coordinated Ge(IV) cation, [(TPFC)-Ge] + , was synthesized through the reaction of (TPFC)Ge−H with [Ph 3 C] + [B(C 6 F 5 ) 4 ] − .…”

Section: ■ Introductionsupporting

confidence: 63%

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Synthesis, Electronic Structure, and Reactivity Studies of a 4-Coordinate Square Planar Germanium(IV) Cation

et al. 2016

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A tetra-coordinate, square planar germanium(IV) cation [(TPFC)Ge](+) (TPFC = tris(pentafluorophenyl)corrole) was synthesized quantitatively by the reaction of (TPFC)Ge-H with [Ph3C](+)[B(C6F5)4](¯). The highly reactive [(TPFC)Ge](+) cation reacted with benzene to form phenyl complex (TPFC)Ge-C6H5 through an electrophilic pathway. The key intermediate, a σ-type germylium-benzene adduct, [(TPFC)Ge(η(1)-C6H6)](+), was isolated and characterized by single-crystal X-ray diffraction. Deprotonation of [(TPFC)Ge(η(1)-C6H6)](+) cation led to the formation of (TPFC)Ge-C6H5. [(TPFC)Ge](+) also reacted with ethylene and cyclopropane in benzene at room temperature to form (TPFC)Ge-CH2CH2C6H5 and (TPFC)Ge-CH2CH2CH2C6H5, respectively. The observed electrophilic reactivity is ascribed to the highly exposed cationic germanium center with novel frontier orbitals comprising two vacant sp-hybridized orbitals that are not conjugated to π-system. The three electron-withdrawing pentafluorophenyl groups on the corrole ligand also enhance the electrophilicity of the cationic germanium corrole.

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Section: Resultssupporting

confidence: 62%

Section: ■ Introductionsupporting

confidence: 63%

Synthesis, Electronic Structure, and Reactivity Studies of a 4-Coordinate Square Planar Germanium(IV) Cation

et al. 2016

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“…Their direct application to estimating reaction and activation free energies for processes even in highly dilute solutions, not to mention the concentrated multicomponent reactive systems commonly encountered in practical catalysis, should be done with certain care. 136,240,241…”

Section: Competition Between Methods and Model Accuracies In Computatimentioning

confidence: 99%

Computational Approach to Molecular Catalysis by 3d Transition Metals: Challenges and Opportunities

et al. 2018

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Computational chemistry provides a versatile toolbox for studying mechanistic details of catalytic reactions and holds promise to deliver practical strategies to enable the rational in silico catalyst design. The versatile reactivity and nontrivial electronic structure effects, common for systems based on 3d transition metals, introduce additional complexity that may represent a particular challenge to the standard computational strategies. In this review, we discuss the challenges and capabilities of modern electronic structure methods for studying the reaction mechanisms promoted by 3d transition metal molecular catalysts. Particular focus will be placed on the ways of addressing the multiconfigurational problem in electronic structure calculations and the role of expert bias in the practical utilization of the available methods. The development of density functionals designed to address transition metals is also discussed. Special emphasis is placed on the methods that account for solvation effects and the multicomponent nature of practical catalytic systems. This is followed by an overview of recent computational studies addressing the mechanistic complexity of catalytic processes by molecular catalysts based on 3d metals. Cases that involve noninnocent ligands, multicomponent reaction systems, metal–ligand and metal–metal cooperativity, as well as modeling complex catalytic systems such as metal–organic frameworks are presented. Conventionally, computational studies on catalytic mechanisms are heavily dependent on the chemical intuition and expert input of the researcher. Recent developments in advanced automated methods for reaction path analysis hold promise for eliminating such human-bias from computational catalysis studies. A brief overview of these approaches is presented in the final section of the review. The paper is closed with general concluding remarks.

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“…In solution this can lead to errors in the calculated entropy of up to 60 kJ/mol. 90 In solution, reactions only take place when reactants approach each other in the same solvent cage, thus, the majority of translational and rotational degrees of freedom is already suppressed due to interactions with solvent molecules. Therefore, the calculation of reactant complexes according to a (hypothetical) situation of not or only weakly interacting reactants is advisable.…”

Section: Computational Detailsmentioning

confidence: 99%

Non-palindromic (C^C^D) gold(iii) pincer complexes are not accessible by intramolecular oxidative addition of biphenylenes – an experimental and quantum chemical study

Feuerstein

Breher

2021

Dalton Trans.

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The Mechanism of E–H (E = N, O) Bond Activation by a Germanium Corrole Complex: A Combined Experimental and Computational Study

Cited by 30 publications

References 66 publications

Synthesis, Electronic Structure, and Reactivity Studies of a 4-Coordinate Square Planar Germanium(IV) Cation

Synthesis, Electronic Structure, and Reactivity Studies of a 4-Coordinate Square Planar Germanium(IV) Cation

Computational Approach to Molecular Catalysis by 3d Transition Metals: Challenges and Opportunities

Non-palindromic (C^C^D) gold(iii) pincer complexes are not accessible by intramolecular oxidative addition of biphenylenes – an experimental and quantum chemical study

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