scholarly journals Force-modulated reductive elimination from platinum(ii) diaryl complexes

2021 ◽  
Author(s):  
Yichen Yu ◽  
Chenxu Wang ◽  
Liqi Wang ◽  
Cai-Li Sun ◽  
Roman Boulatov ◽  
...  
Keyword(s):  
Transition State ◽  
Reductive Elimination ◽  
Mechanical Force ◽  
Elimination Reactions

The influence of mechanical force on the rates of model reductive elimination reactions depends on the structure of the force-transducing ligand and provides a measure of geometry changes upon reaching the transition state.

Diverse mechanisms of carbon-hydrogen bond formation through binuclear reductive elimination reactions

1982 ◽  
Vol 104 (2) ◽  
pp. 619-621 ◽  
Author(s):  
Mario J. Nappa ◽  
Roberto Santi ◽  
Steven P. Diefenbach ◽  
Jack Halpern
Keyword(s):  
Hydrogen Bond ◽  
Bond Formation ◽  
Reductive Elimination ◽  
Hydrogen Bond Formation ◽  
Elimination Reactions

scholarly journals Carbon–sulfur bond formation by reductive elimination of gold(iii) thiolates

2018 ◽  
Vol 47 (18) ◽  
pp. 6333-6343 ◽  
Author(s):  
Lucy Currie ◽  
Luca Rocchigiani ◽  
David L. Hughes ◽  
Manfred Bochmann
Keyword(s):  
Bond Formation ◽  
Reductive Elimination ◽  
Pincer Complexes ◽  
Elimination Reactions ◽  
Sulfur Bond

Thiols were found to cleave Au–C bonds in (C^N^C)gold(iii) pincer complexes and to induce C–S reductive elimination reactions, to give aryl thioethers.

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.

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