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Unraveling the Role of a Flexible Tetradentate Ligand in the Aerobic Oxidative Carbon-Carbon Bond Formation with Palladium Complexes: A Computational Mechanistic Study

Authorized Users Only
2018
Authors
Peng, Qian
Wang, Zengwei
Zarić, Snežana D.
Brothers, Edward N.
Hall, Michael B.
Article (Published version)
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Abstract
Mechanistic details of the aerobic oxidative coupling of methyl groups by a novel (L-Me)Pd-II(Me)(2) complex with the tetradentate ligand, L-Me = N, N-dimethyl-2,11-diaza[3.3]-(2,6)pyridinophane, has been explored by density functional theory calculations. The calculated mechanism sheds light on the role of this ligand's flexibility in several stages of the reaction, especially as the oxidation state of the Pd changes. Ligand flexibility leads to diverse axial coordination modes, and it controls the availability of electrons by modulating the energies of high-lying molecular orbitals, particularly those with major d(z)(2) character. Solvent molecules, particularly water, appear essential in the aerobic oxidation of Pd-II by lowering the energy of the oxygen molecule's unoccupied molecular orbital and stabilizing the Pd-X-O-2 complex. Ligand flexibility and solvent coordination to oxygen are essential to the required spin-crossover for the transformation of high-valent Pd-X-O-2 complexe...s. A methyl cation pathway has been predicted by our calculations in transmetalation between Pd-II and Pd-IV intermediates to be preferred over methyl radical or methyl anion pathways. Combining an axial and equatorial methyl group is preferred in the reductive elimination pathway where roles are played by the ligand's flexibility and the fluxionality of trimethyl groups.

Source:
Journal of the American Chemical Society, 2018, 140, 11, 3929-3939
Publisher:
  • Amer Chemical Soc, Washington
Funding / projects:
  • CHOPTOCOMP - Optimizing Selectivity in C-H Functionalization Through Computational Design (EU-912364)
  • CSA-trust grant
  • Qatar National Research Fund under NPRP [7-297-1-051]
  • 1000-Talent Youth Plan of Tianjin
  • Welch Foundation [A-0648]
  • 1000-Talent Youth Plan of China
  • National Natural Science Foundation of China [21702109]
Note:
  • Peer-reviewed manuscript: http://cherry.chem.bg.ac.rs/handle/123456789/3311
  • Supplementary material: http://cherry.chem.bg.ac.rs/handle/123456789/3310

DOI: 10.1021/jacs.7b11701

ISSN: 0002-7863

PubMed: 29444572

WoS: 000428356000022

Scopus: 2-s2.0-85044361914
[ Google Scholar ]
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URI
https://cherry.chem.bg.ac.rs/handle/123456789/2116
Collections
  • Publikacije
Institution/Community
Hemijski fakultet
TY  - JOUR
AU  - Peng, Qian
AU  - Wang, Zengwei
AU  - Zarić, Snežana D.
AU  - Brothers, Edward N.
AU  - Hall, Michael B.
PY  - 2018
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/2116
AB  - Mechanistic details of the aerobic oxidative coupling of methyl groups by a novel (L-Me)Pd-II(Me)(2) complex with the tetradentate ligand, L-Me = N, N-dimethyl-2,11-diaza[3.3]-(2,6)pyridinophane, has been explored by density functional theory calculations. The calculated mechanism sheds light on the role of this ligand's flexibility in several stages of the reaction, especially as the oxidation state of the Pd changes. Ligand flexibility leads to diverse axial coordination modes, and it controls the availability of electrons by modulating the energies of high-lying molecular orbitals, particularly those with major d(z)(2) character. Solvent molecules, particularly water, appear essential in the aerobic oxidation of Pd-II by lowering the energy of the oxygen molecule's unoccupied molecular orbital and stabilizing the Pd-X-O-2 complex. Ligand flexibility and solvent coordination to oxygen are essential to the required spin-crossover for the transformation of high-valent Pd-X-O-2 complexes. A methyl cation pathway has been predicted by our calculations in transmetalation between Pd-II and Pd-IV intermediates to be preferred over methyl radical or methyl anion pathways. Combining an axial and equatorial methyl group is preferred in the reductive elimination pathway where roles are played by the ligand's flexibility and the fluxionality of trimethyl groups.
PB  - Amer Chemical Soc, Washington
T2  - Journal of the American Chemical Society
T1  - Unraveling the Role of a Flexible Tetradentate Ligand in the Aerobic Oxidative Carbon-Carbon Bond Formation with Palladium Complexes: A Computational Mechanistic Study
VL  - 140
IS  - 11
SP  - 3929
EP  - 3939
DO  - 10.1021/jacs.7b11701
UR  - Kon_3447
ER  - 
@article{
author = "Peng, Qian and Wang, Zengwei and Zarić, Snežana D. and Brothers, Edward N. and Hall, Michael B.",
year = "2018",
abstract = "Mechanistic details of the aerobic oxidative coupling of methyl groups by a novel (L-Me)Pd-II(Me)(2) complex with the tetradentate ligand, L-Me = N, N-dimethyl-2,11-diaza[3.3]-(2,6)pyridinophane, has been explored by density functional theory calculations. The calculated mechanism sheds light on the role of this ligand's flexibility in several stages of the reaction, especially as the oxidation state of the Pd changes. Ligand flexibility leads to diverse axial coordination modes, and it controls the availability of electrons by modulating the energies of high-lying molecular orbitals, particularly those with major d(z)(2) character. Solvent molecules, particularly water, appear essential in the aerobic oxidation of Pd-II by lowering the energy of the oxygen molecule's unoccupied molecular orbital and stabilizing the Pd-X-O-2 complex. Ligand flexibility and solvent coordination to oxygen are essential to the required spin-crossover for the transformation of high-valent Pd-X-O-2 complexes. A methyl cation pathway has been predicted by our calculations in transmetalation between Pd-II and Pd-IV intermediates to be preferred over methyl radical or methyl anion pathways. Combining an axial and equatorial methyl group is preferred in the reductive elimination pathway where roles are played by the ligand's flexibility and the fluxionality of trimethyl groups.",
publisher = "Amer Chemical Soc, Washington",
journal = "Journal of the American Chemical Society",
title = "Unraveling the Role of a Flexible Tetradentate Ligand in the Aerobic Oxidative Carbon-Carbon Bond Formation with Palladium Complexes: A Computational Mechanistic Study",
volume = "140",
number = "11",
pages = "3929-3939",
doi = "10.1021/jacs.7b11701",
url = "Kon_3447"
}
Peng, Q., Wang, Z., Zarić, S. D., Brothers, E. N.,& Hall, M. B.. (2018). Unraveling the Role of a Flexible Tetradentate Ligand in the Aerobic Oxidative Carbon-Carbon Bond Formation with Palladium Complexes: A Computational Mechanistic Study. in Journal of the American Chemical Society
Amer Chemical Soc, Washington., 140(11), 3929-3939.
https://doi.org/10.1021/jacs.7b11701
Kon_3447
Peng Q, Wang Z, Zarić SD, Brothers EN, Hall MB. Unraveling the Role of a Flexible Tetradentate Ligand in the Aerobic Oxidative Carbon-Carbon Bond Formation with Palladium Complexes: A Computational Mechanistic Study. in Journal of the American Chemical Society. 2018;140(11):3929-3939.
doi:10.1021/jacs.7b11701
Kon_3447 .
Peng, Qian, Wang, Zengwei, Zarić, Snežana D., Brothers, Edward N., Hall, Michael B., "Unraveling the Role of a Flexible Tetradentate Ligand in the Aerobic Oxidative Carbon-Carbon Bond Formation with Palladium Complexes: A Computational Mechanistic Study" in Journal of the American Chemical Society, 140, no. 11 (2018):3929-3939,
https://doi.org/10.1021/jacs.7b11701 .,
Kon_3447 .

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