Theoretical studies of oxidative addition and reductive elimination. 3. Carbon-hydrogen and carbon-carbon reductive coupling from palladium and platinum bis(phosphine) complexes

1986 ◽  
Vol 108 (20) ◽  
pp. 6115-6128 ◽  
Author(s):  
John J. Low ◽  
William A. Goddard
Keyword(s):  
Oxidative Addition ◽  
Reductive Elimination ◽  
Theoretical Studies ◽  
Reductive Coupling ◽  
Phosphine Complexes

DFT Study of the Mechanisms of Transition-Metal-Catalyzed Reductive Coupling Reactions

2020 ◽  
Vol 24 (12) ◽  
pp. 1367-1383
Author(s):  
Yuling Wang ◽  
Qinghua Ren
Keyword(s):  
Transition Metal ◽  
Density Functional ◽  
Single Point ◽  
Oxidative Addition ◽  
Density Functional Theory Calculations ◽  
Reductive Elimination ◽  
Coupling Reactions ◽  
Reductive Coupling ◽  
Transition Metal Catalyzed ◽  
Metal Catalyzed

The mechanism studies of transition-metal-catalyzed reductive coupling reactions investigated using Density Functional Theory calculations in the recent ten years have been reviewed. This review introduces the computational mechanism studies of Ni-, Pd-, Cu- and some other metals (Rh, Ti and Zr)-catalyzed reductive coupling reactions and presents the methodology used in these computational mechanism studies. The mechanisms of the transition- metal-catalyzed reductive coupling reactions normally include three main steps: oxidative addition; transmetalation; and reductive elimination or four main steps: the first oxidative addition; reduction; the second oxidative addition; and reductive elimination. The ratelimiting step is most likely the final reductive elimination step in the whole mechanism. Currently, the B3LYP method used in DFT calculations is the most popular choice in the structural geometry optimizations and the M06 method is often used to carry out single-point calculations to refine the energy values. We hope that this review will stimulate more and more experimental and computational combinations and the computational chemistry will significantly contribute to the development of future organic synthesis reactions.

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>

Experimental and theoretical studies on the oxidative addition of palladium(0) to β-chlorovinamidinium salts

Tetrahedron ◽  
2001 ◽  
Vol 57 (24) ◽  
pp. 5061-5066 ◽  
Author(s):  
Ian W Davies ◽  
Jimmy Wu ◽  
Jean-François Marcoux ◽  
Mark Taylor ◽  
David Hughes ◽  
...  
Keyword(s):  
Oxidative Addition ◽  
Theoretical Studies ◽  
Experimental And Theoretical Studies
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