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>

Interconversion of Quadruply and Quintuply Bonded Molybdenum Complexes by Reductive Elimination and Oxidative Addition of Dihydrogen

2013 ◽  
Vol 125 (11) ◽  
pp. 3309-3313 ◽  
Author(s):  
Mario Carrasco ◽  
Natalia Curado ◽  
Celia Maya ◽  
Riccardo Peloso ◽  
Amor Rodríguez ◽  
...  
Keyword(s):  
Oxidative Addition ◽  
Reductive Elimination ◽  
Molybdenum Complexes

Reductive elimination of [AlH2]+ from a cationic Ga-Al dihydride

2021 ◽  
Author(s):  
Jun Okuda ◽  
Louis J. Morris ◽  
Laurent Maron ◽  
Ambre Carpentier
Keyword(s):  
Oxidative Addition ◽  
Reductive Elimination ◽  
Metal Bond ◽  
Metal Metal

Oxidative addition of TMEDA-supported [AlH2]+ to [{BDI}Ga] (BDI = {HC(C(CH3)N(2,6-iPr2-C6H3))2) provides [{BDI}Ga(H)-Al(H)(tmeda)]¬[B(C6H3-3,5-Me2)4] (TMEDA = N,N,N’N’-tetramethylethylene¬diamine) with a covalent metal-metal bond. The reaction is readily reversed by substituting TMEDA for an...

Sign in / Sign up

Export Citation Format

Share Document