scholarly journals Understanding the unique reactivity patterns of nickel/JoSPOphos manifold in the nickel-catalyzed enantioselective C–H cyclization of imidazoles

2021 ◽  
Author(s):  
Jian-Biao Liu ◽  
Xin Wang ◽  
Antonis M. Messinis ◽  
Xiao-Jun Liu ◽  
Rositha Kuniyil ◽  
...  
Keyword(s):  
Hydrogen Transfer ◽  
Oxidative Addition ◽  
Cam Mechanism ◽  
Migratory Insertion

Several unique reactivity patterns of the Ni/JoSPOphos manifold, including facile hydrogen transfer via the two-step oxidative addition/migratory insertion and C(sp2)–H activation via an unconventional σ-CAM mechanism, were disclosed in this work.

Quantifying Steric Effects of α-Diimine Ligands. Oxidative Addition of MeI to Rhodium(I) and Migratory Insertion in Rhodium(III) Complexes

2003 ◽  
Vol 22 (5) ◽  
pp. 1047-1054 ◽  
Author(s):  
Luca Gonsalvi ◽  
Joseph A. Gaunt ◽  
Harry Adams ◽  
Aurora Castro ◽  
Glenn J. Sunley ◽  
...  
Keyword(s):  
Oxidative Addition ◽  
Steric Effects ◽  
Diimine Ligands ◽  
Migratory Insertion

scholarly journals Mechanistic Molecular Motion of Transition-Metal Mediated Beta-Hydride Transfer: Quasiclassical Trajectories Reveal Dynamically Ballistic, Dynamically Unrelaxed, Two Step, and Concerted Mechanisms

2020 ◽  
Author(s):  
Josh Wheeler ◽  
Ryan Carlsen ◽  
Daniel Ess
Keyword(s):  
Transition State ◽  
Density Functional ◽  
Hydrogen Transfer ◽  
Transition States ◽  
Surface Shape ◽  
Concerted Mechanism ◽  
Hydrogen Elimination ◽  
Migratory Insertion ◽  
One Step ◽  
Quasiclassical Trajectories

<div>The transfer of a -hydrogen from a metal-alkyl group to ethylene is a fundamental</div><div>organometallic transformation. Previously proposed mechanisms for this transformation involve either a</div><div>two-step -hydrogen elimination and migratory insertion sequence with a metal hydride intermediate</div><div>or a one-step concerted pathway. Here, we report density functional theory (DFT) quasiclassical direct</div><div>dynamics trajectories that reveal new dynamical mechanisms for the -hydrogen transfer of</div><div>[Cp*RhIII(Et)(ethylene)]</div><div>Despite the DFT energy landscape showing a two-step mechanism with a Rh-H</div><div>intermediate, quasiclassical trajectories commencing from the -hydrogen elimination transition state</div><div>revealed complete dynamical skipping of this intermediate. The skipping occurred either extremely fast</div><div>(typically <100 femtoseconds (fs)) through a dynamically ballistic mechanism or slower through a</div><div>dynamically unrelaxed mechanism. Consistent with trajectories begun at the transition state, all</div><div>trajectories initiated at the Rh-H intermediate show continuation along the reaction coordinate. All of</div><div>these trajectory outcomes are consistent with the Rh-H intermediate <1 kcal/mol stabilized relative to</div><div>the -hydrogen elimination and migratory insertion transition states. For Co, which on the energy</div><div>landscape is a one-step concerted mechanism, trajectories showed extremely fast traversing of the</div><div>transition-state zone (<50 fs), and this concerted mechanism is dynamically different than the Rh</div><div>ballistic mechanism. In contrast to Rh, for Ir, in addition to dynamically ballistic and unrelaxed</div><div>mechanisms, trajectories also stopped at the Ir-H intermediate. This is consistent with an Ir-H</div><div>intermediate that is stabilized by ~3 kcal/mol relative to the -hydrogen elimination and migratory</div><div>insertion transition states. Overall, comparison of Rh to Co and Ir provides understanding of the</div><div>relationship between the energy surface shape and resulting dynamical mechanisms of an</div><div>organometallic transformation.</div>

Hydrofluoroarylation of Alkynes with Ni Catalysts. C–H Activation via Ligand-to-Ligand Hydrogen Transfer, an Alternative to Oxidative Addition

2011 ◽  
Vol 31 (4) ◽  
pp. 1300-1314 ◽  
Author(s):  
Julie Guihaumé ◽  
Stéphanie Halbert ◽  
Odile Eisenstein ◽  
Robin N. Perutz
Keyword(s):  
Hydrogen Transfer ◽  
Oxidative Addition ◽  
Ni Catalysts

Oxidative Addition of Methyl Iodide and CO Migratory Insertion in a Cationic Rhodium Complex of a S,N,S Tridentate Ligand

2003 ◽  
Vol 22 (12) ◽  
pp. 2535-2538 ◽  
Author(s):  
Mauro Bassetti ◽  
Alberto Capone ◽  
Lucilla Mastrofrancesco ◽  
Michela Salamone
Keyword(s):  
Methyl Iodide ◽  
Oxidative Addition ◽  
Rhodium Complex ◽  
Tridentate Ligand ◽  
Migratory Insertion

Kinetic-Mechanistic and Solid-State Study of the Oxidative Addition and Migratory Insertion of Iodomethane to [Rhodium(S,O-BdiPTorN,O-ox)(CO)(PR1R2R3)] Complexes

2018 ◽  
Vol 2018 (32) ◽  
pp. 3615-3625 ◽  
Author(s):  
Stefan Warsink ◽  
P. D. Riekert Kotze ◽  
J. M. Inus Janse van Rensburg ◽  
Johan A. Venter ◽  
Stefanus Otto ◽  
...  
Keyword(s):  
Solid State ◽  
Oxidative Addition ◽  
State Study ◽  
Migratory Insertion

scholarly journals Insights into metal–ligand hydrogen transfer: a square-planar ruthenate complex supported by a tetradentate amino–amido-diolefin ligand

2016 ◽  
Vol 52 (36) ◽  
pp. 6138-6141 ◽  
Author(s):  
Demyan E. Prokopchuk ◽  
Alan J. Lough ◽  
Rafael E. Rodriguez-Lugo ◽  
Robert H. Morris ◽  
Hansjörg Grützmacher
Keyword(s):  
Hydrogen Transfer ◽  
Oxidative Addition ◽  
Square Planar ◽  
Elimination Reactions ◽  
Metal Ligand

A unique square planar anionic ruthenium(0) complex with amido and amine donors undergoes rapid NH oxidative addition/elimination reactions.

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