Unraveling the Role of a Flexible Tetradentate Ligand in the Aerobic Oxidative Carbon-Carbon Bond Formation with Palladium Complexes: A Computational Mechanistic Study
Само за регистроване кориснике
2018
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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.
Извор:
Journal of the American Chemical Society, 2018, 140, 11, 3929-3939Издавач:
- Amer Chemical Soc, Washington
Финансирање / пројекти:
- 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]
Напомена:
- 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
Колекције
Институција/група
Hemijski fakultet / Faculty of ChemistryTY - 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 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" }
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
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 .
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 . .