scholarly journals Calculation of a methane carbon-hydrogen oxidative addition trajectory: comparison to experiment and methane activation by high-valent complexes

1994 ◽  
Vol 116 (1) ◽  
pp. 340-347 ◽  
Author(s):  
Thomas R. Cundari
Keyword(s):  
Oxidative Addition ◽  
Methane Activation ◽  
High Valent ◽  
Methane Carbon

Unexpected Intramolecular Oxidative Addition:  Novel Synthetic Route to High-Valent Group 4 Metallacarboranes Bearing aη6- orη7-Carboranyl Ligand

2002 ◽  
Vol 21 (16) ◽  
pp. 3311-3313 ◽  
Author(s):  
Yaorong Wang ◽  
Haiping Wang ◽  
Hung-Wing Li ◽  
Zuowei Xie
Keyword(s):  
Oxidative Addition ◽  
Synthetic Route ◽  
Group 4 ◽  
High Valent

scholarly journals A radical approach to the copper oxidative addition problem: Trifluoromethylation of bromoarenes

Science ◽  
2018 ◽  
Vol 360 (6392) ◽  
pp. 1010-1014 ◽  
Author(s):  
Chip Le ◽  
Tiffany Q. Chen ◽  
Tao Liang ◽  
Patricia Zhang ◽  
David W. C. MacMillan
Keyword(s):  
Oxidative Addition ◽  
Open Shell ◽  
Past Century ◽  
Aryl Radical ◽  
Aryl Bromides ◽  
Addition Problem ◽  
Molecular Synthesis ◽  
Metal Catalyzed ◽  
High Valent ◽  
Radical Approach

Transition metal–catalyzed arene functionalization has been widely used for molecular synthesis over the past century. In this arena, copper catalysis has long been considered a privileged platform due to the propensity of high-valent copper to undergo reductive elimination with a wide variety of coupling fragments. However, the sluggish nature of oxidative addition has limited copper’s capacity to broadly facilitate haloarene coupling protocols. Here, we demonstrate that this copper oxidative addition problem can be overcome with an aryl radical–capture mechanism, wherein the aryl radical is generated through a silyl radical halogen abstraction. This strategy was applied to a general trifluoromethylation of aryl bromides through dual copper-photoredox catalysis. Mechanistic studies support the formation of an open-shell aryl species.

scholarly journals Oxidation of methane by an N-bridged high-valent diiron–oxo species: electronic structure implications on the reactivity

2015 ◽  
Vol 44 (34) ◽  
pp. 15232-15243 ◽  
Author(s):  
Mursaleem Ansari ◽  
Nidhi Vyas ◽  
Azaj Ansari ◽  
Gopalan Rajaraman
Keyword(s):  
Electronic Structure ◽  
Theoretical Study ◽  
Methane Activation ◽  
Dft Methods ◽  
Oxidation Of Methane ◽  
High Valent

Methane activation by dinuclear high-valent iron–oxo species: do we need two metals to activate such inert bonds? Our theoretical study using DFT methods where electronic structure details and mechanistic aspects are established answers this intriguing question.

Methane activation by ZSM-5-supported transition metal centers

2021 ◽  
Author(s):  
Daniyal Kiani ◽  
Sagar Sourav ◽  
Yadan Tang ◽  
Jonas Baltrusaitis ◽  
Israel E. Wachs
Keyword(s):  
Transition Metal ◽  
Methane Activation ◽  
Group V ◽  
Metal Centers ◽  
Methane Dehydroaromatization

The literature on methane dehydroaromatization (MDA) to benzene using ZSM-5 supported, group V–VIII transition metal-based catalysts (MOx/ZSM-5) is critically reviewed with a focus on in situ and operando molecular insights.

Some Problems in the Oxidative Addition and Binding of an Ethylene to a Transition Metal Center.

1987 ◽  
Vol 6 (4) ◽  
pp. 902-902
Author(s):  
Jerome Silestre ◽  
Maria Calhorda ◽  
Roald Hoffman ◽  
Page Stoutland ◽  
Robert Bergman
Keyword(s):  
Transition Metal ◽  
Oxidative Addition ◽  
Metal Center

Reversible Oxidative-Addition and Reductive-Elimination of Thiophene from a Titanium Complex and Its Thermally-Induced Hydrodesulfurization Chemistry

2019 ◽  
Author(s):  
Alejandra Gomez-Torres ◽  
J. Rolando Aguilar-Calderón ◽  
Carlos Saucedo ◽  
Aldo Jordan ◽  
Alejandro J. Metta-Magaña ◽  
...  
Keyword(s):  
Dft Calculations ◽  
Ring Opening ◽  
Thiophene Ring ◽  
Oxidative Addition ◽  
Reductive Elimination ◽  
Thermally Induced ◽  
Titanium Complex

<p>The masked Ti(II) synthon (<sup>Ket</sup>guan)(<i>η</i><sup>6</sup>-Im<sup>Dipp</sup>N)Ti (<b>1</b>) oxidatively adds across thiophene to give ring-opened (<sup>Ket</sup>guan)(Im<sup>Dipp</sup>N)Ti[<i>κ</i><sup>2</sup>-<i>S</i>(CH)<sub>3</sub><i>C</i>H] (<b>2</b>). Complex <b>2</b> is photosensitive, and upon exposure to light, reductively eliminates thiophene to regenerate <b>1</b> – a rare example of early-metal mediated oxidative-addition/reductive-elimination chemistry. DFT calculations indicate strong titanium π-backdonation to the thiophene π*-orbitals leads to the observed thiophene ring opening across titanium, while a proposed photoinduced LMCT promotes the reverse thiophene elimination from <b>2</b>. Finally, pressurizing solutions of <b>2 </b>with H<sub>2</sub> (150 psi) at 80 °C leads to the hydrodesulfurization of thiophene to give the Ti(IV) sulfide (<sup>Ket</sup>guan)(Im<sup>Dipp</sup>N)Ti(S) (<b>3</b>) and butane. </p>

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