Theoretical Studies on SN2-Reaction of MeBr with Me2CuLi·LiCl. Solvent and Cluster Effects on Oxidative Addition/Reductive Elimination Pathway

1998 ◽  
Vol 120 (32) ◽  
pp. 8273-8274 ◽  
Author(s):  
Eiichi Nakamura ◽  
Seiji Mori ◽  
Keiji Morokuma
Keyword(s):  
Oxidative Addition ◽  
Reductive Elimination ◽  
Theoretical Studies ◽  
Sn2 Reaction ◽  
Elimination Pathway

scholarly journals Dramatic mechanistic switch in Sn/AuI group exchanges: transmetalation vs. oxidative addition

2016 ◽  
Vol 52 (23) ◽  
pp. 4305-4308 ◽  
Author(s):  
D. Carrasco ◽  
M. García-Melchor ◽  
J. A. Casares ◽  
P. Espinet
Keyword(s):  
Oxidative Addition ◽  
Reductive Elimination ◽  
Concerted Mechanism ◽  
Elimination Pathway

The mechanism of Ph/X exchange in reactions involving SnPhnBu3 and [AuXL] complexes switches dramatically from the usual concerted mechanism involving Ar/X mixed bridges when X = Cl, to an unexpected oxidative addition/reductive elimination pathway via an AuIII intermediate when X = vinyl.

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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