scholarly journals Concerted aryl-sulfur reductive elimination from PNP pincer-supported Co(iii) and subsequent Co(i)/Co(iii) comproportionation

2020 ◽  
Vol 11 (23) ◽  
pp. 6075-6084 ◽  
Author(s):  
Bryan J. Foley ◽  
Chandra Mouli Palit ◽  
Nattamai Bhuvanesh ◽  
Jia Zhou ◽  
Oleg V. Ozerov
Keyword(s):  
Computational Study ◽  
Reductive Elimination ◽  
Pincer Ligand

This report discloses a combined experimental and computational study aimed at understanding C–S reductive elimination from Co(iii) supported by a diarylamido/bis(phosphine) PNP pincer ligand.

Computational Study of the Palladium-Catalyzed Carbonylative Synthesis of Aromatic Acid Chlorides: The Synergistic Effect of Pt Bu3 and CO on Reductive Elimination

2016 ◽  
Vol 22 (42) ◽  
pp. 15107-15118 ◽  
Author(s):  
Jeffrey S. Quesnel ◽  
Salvador Moncho ◽  
Kai E. O. Ylijoki ◽  
Gerardo Martin Torres ◽  
Edward N. Brothers ◽  
...  
Keyword(s):  
Synergistic Effect ◽  
Computational Study ◽  
Reductive Elimination ◽  
Aromatic Acid ◽  
Acid Chlorides ◽  
Palladium Catalyzed

Selectivity in carbon–carbon coupling reactions at palladium(IV) and platinum(IV)

2019 ◽  
Vol 97 (7) ◽  
pp. 529-537 ◽  
Author(s):  
Richard J. Puddephatt
Keyword(s):  
Activation Energy ◽  
Transition State ◽  
Computational Study ◽  
Bond Formation ◽  
Reductive Elimination ◽  
Organometallic Complexes ◽  
Axial Position ◽  
Coupling Reactions ◽  
Methyl Group ◽  
Trigonal Bipyramidal

The isomerization and reductive elimination reactions from octahedral organometallic complexes of palladium(IV) and platinum(IV) usually occur through five-coordinate intermediates that cannot be directly detected. This paper reports a computational study of five-coordinate complexes of formulae [PtMe3(bipy)]+, [PtMe2Ph(bipy)]+, and [PtMe(CH2CMe2C6H4)(bipy)]+ (M = Pd or Pt, bipy = 2,2′-bipyridine), particularly with respect to reactivity and selectivity in reductive elimination. All of the complexes are predicted to have square pyramidal structures with the bipy and two R groups in the equatorial positions and one R group in the axial position, and axial–equatorial exchange occurs by a pairwise mechanism, with the transition state having a pinched trigonal bipyramidal (PTBP) stereochemistry, with one nitrogen and two R groups in the trigonal plane. The activation energy for isomerization is lower than that for reductive elimination in all cases. For the complexes [MMe2Ph(bipy)]+, the activation energies for reductive elimination with Me–Me or Me–Ph coupling are similar. For the complexes [MMe(CH2CMe2C6H4)(bipy)]+, the reductive elimination with Me–C6H4 bond formation from the isomer with the methyl group in the axial position is predicted and is attributed to it having the best conformation of the Me and C6H4 groups for C–C bond formation. In all cases, the selectivity for reductive elimination is similar for M = Pd or Pt, but reactivity is higher for M = Pd. The relevance of this work to selectivity in catalysis is discussed.

Reductive Elimination of ArCF3 from Bidentate PdII Complexes: A Computational Study

2011 ◽  
Vol 17 (44) ◽  
pp. 12340-12346 ◽  
Author(s):  
Philipp Anstaett ◽  
Franziska Schoenebeck
Keyword(s):  
Computational Study ◽  
Reductive Elimination

scholarly journals Experimental and computational study of alkane dehydrogenation catalyzed by a carbazolide-based rhodium PNP pincer complex

2016 ◽  
Vol 7 (4) ◽  
pp. 2579-2586 ◽  
Author(s):  
David Bézier ◽  
Changjian Guan ◽  
Karsten Krogh-Jespersen ◽  
Alan S. Goldman ◽  
Maurice Brookhart
Keyword(s):  
Computational Study ◽  
Rhodium Complex ◽  
Pincer Ligand ◽  
Alkane Dehydrogenation ◽  
Pincer Complex

A rhodium complex based on the bis-phosphine carbazolide pincer ligand was investigated in the context of alkane dehydrogenation and in comparison with its iridium analogue.

scholarly journals Copper-Catalyzed Eglinton Oxidative Homocoupling of Terminal Alkynes: A Computational Study

2015 ◽  
Vol 2015 ◽  
pp. 1-8 ◽  
Author(s):  
Jesús Jover
Keyword(s):  
Computational Study ◽  
Reductive Elimination ◽  
Terminal Alkynes ◽  
Dft Methods ◽  
Rate Limiting Step ◽  
Limiting Step ◽  
Rate Limiting ◽  
Oxidative Homocoupling

The copper(II) acetate mediated oxidative homocoupling of terminal alkynes, namely, the Eglinton coupling, has been studied with DFT methods. The mechanism of the whole reaction has been modeled using phenylacetylene as substrate. The obtained results indicate that, in contrast to some classical proposals, the reaction does not involve the formation of free alkynyl radicals and proceeds by the dimerization of copper(II) alkynyl complexes followed by a bimetallic reductive elimination. The calculations demonstrate that the rate limiting-step of the reaction is the alkyne deprotonation and that more acidic substrates provide faster reactions, in agreement with the experimental observations.

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