Warning: Undefined array key "mm" in /www/wwwroot/www.ai-bt.com/si.php on line 10 Deprecated: trim(): Passing null to parameter #1 ($string) of type string is deprecated in /www/wwwroot/www.ai-bt.com/si.php on line 10 Exchange-enhanced reactivity in bond activation by metal-oxo enzymes and synthetic reagents.

Literature DB >> 21160512

Exchange-enhanced reactivity in bond activation by metal-oxo enzymes and synthetic reagents.

Sason Shaik¹, Hui Chen, Deepa Janardanan.

Abstract

Reactivity principles based on orbital overlap and bonding/antibonding interactions are well established to describe the reactivity of organic species, and atomic structures are typically predicted by Hund's rules to have maximum single-electron occupancy of degenerate orbitals in the ground state. Here, we extend the role of exchange to transition states and discuss how, for reactions and kinetics of bioinorganic species, the analogue of Hund's rules is exchange-controlled reactivity. Pathways that increase the number of unpaired and spin-identical electrons on a metal centre will be favoured by exchange stabilization. Such exchange-enhanced reactivity endows transition states with a stereochemistry different from that observed in cases that are not exchange-enhanced, and is in good agreement with the reactivity observed for iron-based enzymes and synthetic analogues. We discuss the interplay between orbital- and exchange-controlled principles, and how this depends on the identity of the transition metal, its oxidation number and its coordination sphere.

Entities: Chemical

Mesh：

Substances：

Year: 2010 PMID： 21160512 DOI： 10.1038/nchem.943

Source DB: PubMed Journal: Nat Chem ISSN： 1755-4330 Impact factor: 24.427

41 in total

1. Two-state reactivity in alkane hydroxylation by non-heme iron-oxo complexes.

Authors: Hajime Hirao; Devesh Kumar; Lawrence Que; Sason Shaik
Journal: J Am Chem Soc Date: 2006-07-05 Impact factor: 15.419

Review 2. Finding intermediates in the O2 activation pathways of non-heme iron oxygenases.

Authors: E G Kovaleva; M B Neibergall; S Chakrabarty; J D Lipscomb
Journal: Acc Chem Res Date: 2007-06-14 Impact factor: 22.384

3. Origin of the correlation of the rate constant of substrate hydroxylation by nonheme iron(IV)-oxo complexes with the bond-dissociation energy of the C-H bond of the substrate.

Authors: Reza Latifi; Mojtaba Bagherzadeh; Sam P de Visser
Journal: Chemistry Date: 2009-07-06 Impact factor: 5.236

4. The fundamental role of exchange-enhanced reactivity in C-H activation by S=2 oxo iron(IV) complexes.

Authors: Deepa Janardanan; Yong Wang; Patric Schyman; Lawrence Que; Sason Shaik
Journal: Angew Chem Int Ed Engl Date: 2010-04-26 Impact factor: 15.336

Review 5. P450 enzymes: their structure, reactivity, and selectivity-modeled by QM/MM calculations.

Authors: Sason Shaik; Shimrit Cohen; Yong Wang; Hui Chen; Devesh Kumar; Walter Thiel
Journal: Chem Rev Date: 2010-02-10 Impact factor: 60.622

6. (Salen)Mn(III)-catalyzed epoxidation reaction as a multichannel process with different spin states. Electronic tuning of asymmetric catalysis: a theoretical study.

Authors: Y G Abashkin; J R Collins; S K Burt
Journal: Inorg Chem Date: 2001-07-30 Impact factor: 5.165

7. Spectroscopic and electronic structure studies of aromatic electrophilic attack and hydrogen-atom abstraction by non-heme iron enzymes.

Authors: Michael L Neidig; Andrea Decker; Oliver W Choroba; Fanglu Huang; Michael Kavana; Graham R Moran; Jonathan B Spencer; Edward I Solomon
Journal: Proc Natl Acad Sci U S A Date: 2006-08-18 Impact factor: 11.205

8. Spin forbidden chemical reactions of transition metal compounds. New ideas and new computational challenges.

Authors: Rinaldo Poli; Jeremy N Harvey
Journal: Chem Soc Rev Date: 2003-01 Impact factor: 54.564

Review 9. Reactivity of high-valent iron-oxo species in enzymes and synthetic reagents: a tale of many states.

Authors: Sason Shaik; Hajime Hirao; Devesh Kumar
Journal: Acc Chem Res Date: 2007-05-09 Impact factor: 22.384

10. Mechanism of dioxygen cleavage in tetrahydrobiopterin-dependent amino acid hydroxylases.

Authors: Arianna Bassan; Margareta R A Blomberg; Per E M Siegbahn
Journal: Chemistry Date: 2003-01-03 Impact factor: 5.236

38 in total

1. Dichotomous hydrogen atom transfer vs proton-coupled electron transfer during activation of X-H bonds (X = C, N, O) by nonheme iron-oxo complexes of variable basicity.

Authors: Dandamudi Usharani; David C Lacy; A S Borovik; Sason Shaik
Journal: J Am Chem Soc Date: 2013-11-04 Impact factor: 15.419

2. Facile and Reversible Formation of Iron(III)-Oxo-Cerium(IV) Adducts from Nonheme Oxoiron(IV) Complexes and Cerium(III).

Authors: Apparao Draksharapu; Waqas Rasheed; Johannes E M N Klein; Lawrence Que
Journal: Angew Chem Int Ed Engl Date: 2017-06-27 Impact factor: 15.336

3. Oriented electric fields as future smart reagents in chemistry.

Authors: Sason Shaik; Debasish Mandal; Rajeev Ramanan
Journal: Nat Chem Date: 2016-11-22 Impact factor: 24.427

4. The oxidation of cyclo-olefin by the S = 2 ground-state complex [Fe^IV(O)(TQA)(NCMe)]².

Authors: Zixian Li; Yi Wang; Wenzhi Li; Qingyue Li; Fan Li; Ziqing Gao; Xu Fei; Jing Tian; Liang Dong
Journal: J Biol Inorg Chem Date: 2020-03-04 Impact factor: 3.358

Review 5. VTST/MT studies of the catalytic mechanism of C-H activation by transition metal complexes with [Cu₂(μ-O₂)], [Fe₂(μ-O₂)] and Fe(IV)-O cores based on DFT potential energy surfaces.

Authors: Yongho Kim; Binh Khanh Mai; Sumin Park
Journal: J Biol Inorg Chem Date: 2017-01-16 Impact factor: 3.358

Exchange-enhanced reactivity in bond activation by metal-oxo enzymes and synthetic reagents.

1. Two-state reactivity in alkane hydroxylation by non-heme iron-oxo complexes.

Review 2. Finding intermediates in the O2 activation pathways of non-heme iron oxygenases.

3. Origin of the correlation of the rate constant of substrate hydroxylation by nonheme iron(IV)-oxo complexes with the bond-dissociation energy of the C-H bond of the substrate.

4. The fundamental role of exchange-enhanced reactivity in C-H activation by S=2 oxo iron(IV) complexes.

Review 5. P450 enzymes: their structure, reactivity, and selectivity-modeled by QM/MM calculations.

6. (Salen)Mn(III)-catalyzed epoxidation reaction as a multichannel process with different spin states. Electronic tuning of asymmetric catalysis: a theoretical study.

7. Spectroscopic and electronic structure studies of aromatic electrophilic attack and hydrogen-atom abstraction by non-heme iron enzymes.

8. Spin forbidden chemical reactions of transition metal compounds. New ideas and new computational challenges.

Review 9. Reactivity of high-valent iron-oxo species in enzymes and synthetic reagents: a tale of many states.

10. Mechanism of dioxygen cleavage in tetrahydrobiopterin-dependent amino acid hydroxylases.

1. Dichotomous hydrogen atom transfer vs proton-coupled electron transfer during activation of X-H bonds (X = C, N, O) by nonheme iron-oxo complexes of variable basicity.

2. Facile and Reversible Formation of Iron(III)-Oxo-Cerium(IV) Adducts from Nonheme Oxoiron(IV) Complexes and Cerium(III).

3. Oriented electric fields as future smart reagents in chemistry.

4. The oxidation of cyclo-olefin by the S = 2 ground-state complex [Fe^IV(O)(TQA)(NCMe)]².

Review 5. VTST/MT studies of the catalytic mechanism of C-H activation by transition metal complexes with [Cu₂(μ-O₂)], [Fe₂(μ-O₂)] and Fe(IV)-O cores based on DFT potential energy surfaces.

6. Do Spin State and Spin Density Affect Hydrogen Atom Transfer Reactivity?

7. A Highly Reactive Oxoiron(IV) Complex Supported by a Bioinspired N₃ O Macrocyclic Ligand.

8. Exploring the potential of iron to replace ruthenium in photosensitizers: a computational study.

Review 9. Oxygen Activation and Radical Transformations in Heme Proteins and Metalloporphyrins.

10. Nonheme Oxoiron(IV) Complexes of Pentadentate N5 Ligands: Spectroscopy, Electrochemistry, and Oxidative Reactivity.

Review 2. Finding intermediates in the O2 activation pathways of non-heme iron oxygenases.

Review 5. P450 enzymes: their structure, reactivity, and selectivity-modeled by QM/MM calculations.

Review 9. Reactivity of high-valent iron-oxo species in enzymes and synthetic reagents: a tale of many states.

Review 5. VTST/MT studies of the catalytic mechanism of C-H activation by transition metal complexes with [Cu2(μ-O2)], [Fe2(μ-O2)] and Fe(IV)-O cores based on DFT potential energy surfaces.

Review 9. Oxygen Activation and Radical Transformations in Heme Proteins and Metalloporphyrins.

Review 5. VTST/MT studies of the catalytic mechanism of C-H activation by transition metal complexes with [Cu₂(μ-O₂)], [Fe₂(μ-O₂)] and Fe(IV)-O cores based on DFT potential energy surfaces.