C–H bond activation <i>via</i> concerted metalation–deprotonation at a palladium(<scp>iii</scp>) center

Mirica, Liviu M.; Bouley, Bailey S.; Tang, Fenghzi; Bae, Dae Young

doi:10.1039/d3sc00034f

Cited by 4 publications

(3 citation statements)

References 65 publications

(92 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…6–8 Because these C–H activation steps are often involved in the rate-limiting step, their intimate mechanisms have been extensively investigated by experimental and computational methods and the relevance of carboxylate assistance has been clearly recognized. 9–13…”

Section: Introductionmentioning

confidence: 99%

“…[6][7][8] Because these C-H activation steps are often involved in the rate-limiting step, their intimate mechanisms have been extensively investigated by experimental and computational methods and the relevance of carboxylate assistance has been clearly recognized. [9][10][11][12][13] Highly regioselective carboxylate-assisted C-H activation processes can be accomplished, [14][15][16][17] particularly for ligands that contain chemical groups able to coordinate to Pd. These so-called directing groups 18 are able to bring the metal into the vicinity of a particular C-H bond.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Ion mobility mass spectrometry uncovers regioselectivity in the carboxylate-assisted C–H activation of palladium N-heterocyclic carbene complexes

Ibáñez-Ibáñez,

Mollar-Cuni,

Apaloo-Messan

et al. 2024

Dalton Trans.

View full text Add to dashboard Cite

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Ion mobility mass spectrometry uncovers regioselectivity in the carboxylate-assisted C–H activation of palladium N-heterocyclic carbene complexes

Ibáñez-Ibáñez,

Mollar-Cuni,

Apaloo-Messan

et al. 2024

Dalton Trans.

View full text Add to dashboard Cite

show abstract

“…While this introduces complex mechanistic intricacies and undesired sidereactions, it also enables catalytic transformations unavailable for their heavier congeners, thereby significantly expanding the applications of transition metal catalysis. (2)(3)(4)(5).…”

Section: Introductionmentioning

confidence: 99%

An Open-Shell IrII/IrIV Redox Couple Outperforms the Conventional IrI/IrIII Pair for the Catalytic Isomerization of Olefins

Pita-Milleiro,

Hidalgo,

Moreno

et al. 2024

Preprint

View full text Add to dashboard Cite

The chemistry of mononuclear open-shell complexes of precious transition metals is largely underdeveloped, which contrasts with that of first-row transition metals and their catalytic applications. This is particularly true for IrII complexes and its almost inexistent participation in catalysis. Here we report the synthesis and characterization of a small family of mononuclear IrII metalloradicals constructed around a POCOP pincer ligand (POCOP = C6H3-2,6-(OP(tBu)2)2) and explore their performance as catalysts for olefin isomerization, a fundamental process for alkane metathesis. These paramagnetic species are up to 20 times more active than their diamagnetic IrI analogues. Strikingly, the elementary steps involved in the catalytic action of both IrI and IrII are virtually identical according to our computational investigations. However, the proposed unprecedented IrII/IrIV redox cycle presents faster kinetics than the traditional IrI/IrIII route due to much lower barriers for the key oxidative addition and reductive elimination events, a feature that we rationalize by means of the Activation Strain Model-Energy Decomposition Analysis-approach. In essence, we report the first example of a catalytic system based on a mononuclear IrII/IrIV redox couple, a fundamental contribution to the underexplored chemistry of IrII compounds that stresses the necessity to broaden the catalyst search and design guidelines beyond conventional redox cycles, including those based on platinum-group metals.

show abstract

Mechanistic insights into C(sp2)-H activation in 1-Phenyl-4-vinyl-1H-1,2,3-triazole derivatives: a theoretical study with palladium acetate catalyst

Fogos,

Lessa,

de Carvalho da Silva

et al. 2024

J Mol Model

View full text Add to dashboard Cite

ContextThe activation of C-H bonds is a fundamental process in synthetic organic chemistry, which enables their replacement by highly reactive functional groups. Coordination compounds serve as effective catalysts for this purpose, as they facilitate chemical transformations by interacting with C-H bonds. A comprehensive understanding of the mechanism of activation of this type of bond lays the foundation for the development of e cient protocols for cross-coupling reactions. We explored the activation of C(sp 2 )-H bonds in 1-Phenyl-4-vinyl-1H-1,2,3-triazole derivatives with CH 3 , OCH 3 and NO 2 substituents in the para position of the phenyl ring, using palladium acetate as catalyst. The studied reaction is the rst step for subsequent conjugation of the triazoles with naphthoquinones in a Heck-type reaction to create a C-C bond. The basic nitrogen atoms of the 1,2,3-triazole coordinate preferentially with the cationic palladium center to form an activated species. A concerted proton transfer from the terminal vinyl carbon to one of the acetate ligands with low activation energy is the main step for the C(sp 2 )-H activation. This study offers signi cant mechanistic insights for enhancing the effectiveness of C(sp 2 )-H activation protocols in organic synthesis. MethodsAll calculations were performed using the Gaussian 09 software package and density functional theory (DFT). The structures of all reaction path components were fully optimized using the CAM-B3LYP functional with the Def2-SVP basis set. The optimized geometries were analyzed by computing the second-order Hessian matrix to con rm whether the corresponding structure is a minimum or a true transition state. To account for solvent effects, the Polarizable Continuum Model of the Integral Equation Formalism (IEFPCM) with water as the solvent was used.

show abstract

C–H bond activation via concerted metalation–deprotonation at a palladium(iii) center

Abstract: Herein we report the direct observation of C-H bond activation at an isolated mononuclear Pd(III) center. The oxidation of the Pd(II) complex (MeN4)PdII(neophyl)Cl (neophyl = -CH2C(CH3)2Ph; MeN4 = N,N′-di-tert-butyl-2,11-diaza[3.3](2,6)pyridinophane) using...

Cited by 4 publications

References 65 publications

Ion mobility mass spectrometry uncovers regioselectivity in the carboxylate-assisted C–H activation of palladium N-heterocyclic carbene complexes

Ion mobility mass spectrometry uncovers regioselectivity in the carboxylate-assisted C–H activation of palladium N-heterocyclic carbene complexes

An Open-Shell IrII/IrIV Redox Couple Outperforms the Conventional IrI/IrIII Pair for the Catalytic Isomerization of Olefins

Mechanistic insights into C(sp2)-H activation in 1-Phenyl-4-vinyl-1H-1,2,3-triazole derivatives: a theoretical study with palladium acetate catalyst

Contact Info

Product

Resources

About