TY  - JOUR
AU  - Guan, Jia
AU  - Wriglesworth, Alisdair
AU  - Sun, Xue Zhong
AU  - Brothers, Edward N.
AU  - Zarić, Snežana D.
AU  - Evans, Meagan E.
AU  - Jones, William D.
AU  - Towrie, Michael
AU  - Hall, Michael B.
AU  - George, Michael W.
PY  - 2018
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/2893
AB  - Carbon-hydrogen bond activation of alkanes by Tp'Rh(CNR) (Tp' = Tp = trispyrazolylborate or Tp* = tris(3,5- dimethylpyrazolyl)borate) were followed by time-resolved infrared spectroscopy (TRIR) in the upsilon(CNR) and upsilon(B-H) spectral regions on Tp*Rh(CNCH2CMe3), and their reaction mechanisms were modeled by density functional theory (DFT) on TpRh(CNMe). The major intermediate species were: kappa(3)-eta(1)-alkane complex (1); kappa(2)-kappa(2)-alkane complex (2); and kappa(3)-alkyl hydride (3). Calculations predict that the barrier between 1 and 2 arises from a triplet-singlet crossing and intermediate 2 proceeds over the rate-determining C-H activation barrier to give the final product 3. The activation lifetimes measured for the Tp*Rh(CNR) and Tp*Rh(CO) fragments with n-heptane and four cycloalkanes (C5H10, C6H12, C7H14, and C8H16) increase with alkanes size and show a dramatic increase between C6H12 and C7H14. A similar step-like behavior was observed previously with CpRh(CO) and Cp*Rh(CO) fragments and is attributed to the wider difference in C-H bonds that appear at C7H14. However, Tp'Rh(CNR) and Tp'Rh(CO) fragments have much longer absolute lifetimes compared to those of CpRh(CO) and Cp*Rh(CO) fragments, because the reduced electron density in dechelated kappa(2)-eta(2)-alkane Tp' complexes stabilizes the d(8) Rh(I) in a square-planar geometry and weakens the metal's ability for oxidative addition of the C-H bond. Further, the Tp'Rh(CNR) fragment has significantly slower rates of C-H activation in comparison to the Tp'Rh(CO) fragment for the larger cycloalkanes, because the steric bulk of the neopentyl isocyanide ligand hinders the rechelation in kappa(2)-Tp'Rh(CNR)(cycloalkane) species and results in the C-H activation without the assistance of the rechelation.
PB  - Amer Chemical Soc, Washington
T2  - Journal of the American Chemical Society
T1  - Probing the Carbon-Hydrogen Activation of Alkanes Following Photolysis of Tp'Rh(CNR)(carbodiimide): A Computational and Time Resolved Infrared Spectroscopic Study
VL  - 140
IS  - 5
SP  - 1842
EP  - 1854
DO  - 10.1021/jacs.7b12152
ER  - 

@article{
author = "Guan, Jia and Wriglesworth, Alisdair and Sun, Xue Zhong and Brothers, Edward N. and Zarić, Snežana D. and Evans, Meagan E. and Jones, William D. and Towrie, Michael and Hall, Michael B. and George, Michael W.",
year = "2018",
abstract = "Carbon-hydrogen bond activation of alkanes by Tp'Rh(CNR) (Tp' = Tp = trispyrazolylborate or Tp* = tris(3,5- dimethylpyrazolyl)borate) were followed by time-resolved infrared spectroscopy (TRIR) in the upsilon(CNR) and upsilon(B-H) spectral regions on Tp*Rh(CNCH2CMe3), and their reaction mechanisms were modeled by density functional theory (DFT) on TpRh(CNMe). The major intermediate species were: kappa(3)-eta(1)-alkane complex (1); kappa(2)-kappa(2)-alkane complex (2); and kappa(3)-alkyl hydride (3). Calculations predict that the barrier between 1 and 2 arises from a triplet-singlet crossing and intermediate 2 proceeds over the rate-determining C-H activation barrier to give the final product 3. The activation lifetimes measured for the Tp*Rh(CNR) and Tp*Rh(CO) fragments with n-heptane and four cycloalkanes (C5H10, C6H12, C7H14, and C8H16) increase with alkanes size and show a dramatic increase between C6H12 and C7H14. A similar step-like behavior was observed previously with CpRh(CO) and Cp*Rh(CO) fragments and is attributed to the wider difference in C-H bonds that appear at C7H14. However, Tp'Rh(CNR) and Tp'Rh(CO) fragments have much longer absolute lifetimes compared to those of CpRh(CO) and Cp*Rh(CO) fragments, because the reduced electron density in dechelated kappa(2)-eta(2)-alkane Tp' complexes stabilizes the d(8) Rh(I) in a square-planar geometry and weakens the metal's ability for oxidative addition of the C-H bond. Further, the Tp'Rh(CNR) fragment has significantly slower rates of C-H activation in comparison to the Tp'Rh(CO) fragment for the larger cycloalkanes, because the steric bulk of the neopentyl isocyanide ligand hinders the rechelation in kappa(2)-Tp'Rh(CNR)(cycloalkane) species and results in the C-H activation without the assistance of the rechelation.",
publisher = "Amer Chemical Soc, Washington",
journal = "Journal of the American Chemical Society",
title = "Probing the Carbon-Hydrogen Activation of Alkanes Following Photolysis of Tp'Rh(CNR)(carbodiimide): A Computational and Time Resolved Infrared Spectroscopic Study",
volume = "140",
number = "5",
pages = "1842-1854",
doi = "10.1021/jacs.7b12152"
}

Guan, J., Wriglesworth, A., Sun, X. Z., Brothers, E. N., Zarić, S. D., Evans, M. E., Jones, W. D., Towrie, M., Hall, M. B.,& George, M. W.. (2018). Probing the Carbon-Hydrogen Activation of Alkanes Following Photolysis of Tp'Rh(CNR)(carbodiimide): A Computational and Time Resolved Infrared Spectroscopic Study. in Journal of the American Chemical Society
Amer Chemical Soc, Washington., 140(5), 1842-1854.
https://doi.org/10.1021/jacs.7b12152

Guan J, Wriglesworth A, Sun XZ, Brothers EN, Zarić SD, Evans ME, Jones WD, Towrie M, Hall MB, George MW. Probing the Carbon-Hydrogen Activation of Alkanes Following Photolysis of Tp'Rh(CNR)(carbodiimide): A Computational and Time Resolved Infrared Spectroscopic Study. in Journal of the American Chemical Society. 2018;140(5):1842-1854.
doi:10.1021/jacs.7b12152 .

Guan, Jia, Wriglesworth, Alisdair, Sun, Xue Zhong, Brothers, Edward N., Zarić, Snežana D., Evans, Meagan E., Jones, William D., Towrie, Michael, Hall, Michael B., George, Michael W., "Probing the Carbon-Hydrogen Activation of Alkanes Following Photolysis of Tp'Rh(CNR)(carbodiimide): A Computational and Time Resolved Infrared Spectroscopic Study" in Journal of the American Chemical Society, 140, no. 5 (2018):1842-1854,
https://doi.org/10.1021/jacs.7b12152 . .

TY  - DATA
AU  - Guan, Jia
AU  - Wriglesworth, Alisdair
AU  - Sun, Xue Zhong
AU  - Brothers, Edward N.
AU  - Zarić, Snežana D.
AU  - Evans, Meagan E.
AU  - Jones, William D.
AU  - Towrie, Michael
AU  - Hall, Michael B.
AU  - George, Michael W.
PY  - 2018
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/2942
PB  - Amer Chemical Soc, Washington
T2  - Journal of the American Chemical Society
T1  - Supplementary data for the article: Guan, J.; Wriglesworth, A.; Sun, X. Z.; Brothers, E. N.; Zarić, S. D.; Evans, M. E.; Jones, W. D.; Towrie, M.; Hall, M. B.; George, M. W. Probing the Carbon-Hydrogen Activation of Alkanes Following Photolysis of Tp′Rh(CNR)(Carbodiimide): A Computational and Time-Resolved Infrared Spectroscopic Study. Journal of the American Chemical Society 2018, 140 (5), 1842–1854. https://doi.org/10.1021/jacs.7b12152
UR  - https://hdl.handle.net/21.15107/rcub_cherry_2942
ER  - 

@misc{
author = "Guan, Jia and Wriglesworth, Alisdair and Sun, Xue Zhong and Brothers, Edward N. and Zarić, Snežana D. and Evans, Meagan E. and Jones, William D. and Towrie, Michael and Hall, Michael B. and George, Michael W.",
year = "2018",
publisher = "Amer Chemical Soc, Washington",
journal = "Journal of the American Chemical Society",
title = "Supplementary data for the article: Guan, J.; Wriglesworth, A.; Sun, X. Z.; Brothers, E. N.; Zarić, S. D.; Evans, M. E.; Jones, W. D.; Towrie, M.; Hall, M. B.; George, M. W. Probing the Carbon-Hydrogen Activation of Alkanes Following Photolysis of Tp′Rh(CNR)(Carbodiimide): A Computational and Time-Resolved Infrared Spectroscopic Study. Journal of the American Chemical Society 2018, 140 (5), 1842–1854. https://doi.org/10.1021/jacs.7b12152",
url = "https://hdl.handle.net/21.15107/rcub_cherry_2942"
}

Guan, J., Wriglesworth, A., Sun, X. Z., Brothers, E. N., Zarić, S. D., Evans, M. E., Jones, W. D., Towrie, M., Hall, M. B.,& George, M. W.. (2018). Supplementary data for the article: Guan, J.; Wriglesworth, A.; Sun, X. Z.; Brothers, E. N.; Zarić, S. D.; Evans, M. E.; Jones, W. D.; Towrie, M.; Hall, M. B.; George, M. W. Probing the Carbon-Hydrogen Activation of Alkanes Following Photolysis of Tp′Rh(CNR)(Carbodiimide): A Computational and Time-Resolved Infrared Spectroscopic Study. Journal of the American Chemical Society 2018, 140 (5), 1842–1854. https://doi.org/10.1021/jacs.7b12152. in Journal of the American Chemical Society
Amer Chemical Soc, Washington..
https://hdl.handle.net/21.15107/rcub_cherry_2942

Guan J, Wriglesworth A, Sun XZ, Brothers EN, Zarić SD, Evans ME, Jones WD, Towrie M, Hall MB, George MW. Supplementary data for the article: Guan, J.; Wriglesworth, A.; Sun, X. Z.; Brothers, E. N.; Zarić, S. D.; Evans, M. E.; Jones, W. D.; Towrie, M.; Hall, M. B.; George, M. W. Probing the Carbon-Hydrogen Activation of Alkanes Following Photolysis of Tp′Rh(CNR)(Carbodiimide): A Computational and Time-Resolved Infrared Spectroscopic Study. Journal of the American Chemical Society 2018, 140 (5), 1842–1854. https://doi.org/10.1021/jacs.7b12152. in Journal of the American Chemical Society. 2018;.
https://hdl.handle.net/21.15107/rcub_cherry_2942 .

Guan, Jia, Wriglesworth, Alisdair, Sun, Xue Zhong, Brothers, Edward N., Zarić, Snežana D., Evans, Meagan E., Jones, William D., Towrie, Michael, Hall, Michael B., George, Michael W., "Supplementary data for the article: Guan, J.; Wriglesworth, A.; Sun, X. Z.; Brothers, E. N.; Zarić, S. D.; Evans, M. E.; Jones, W. D.; Towrie, M.; Hall, M. B.; George, M. W. Probing the Carbon-Hydrogen Activation of Alkanes Following Photolysis of Tp′Rh(CNR)(Carbodiimide): A Computational and Time-Resolved Infrared Spectroscopic Study. Journal of the American Chemical Society 2018, 140 (5), 1842–1854. https://doi.org/10.1021/jacs.7b12152" in Journal of the American Chemical Society (2018),
https://hdl.handle.net/21.15107/rcub_cherry_2942 .

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
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 . .

TY  - DATA
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/123456789/3310
PB  - Amer Chemical Soc, Washington
T2  - Journal of the American Chemical Society
T1  - Supplementary data for the article: Peng, Q.; Wang, Z.; Zarić, S. D.; Brothers, E. N.; Hall, M. B. Unraveling the Role of a Flexible Tetradentate Ligand in the Aerobic Oxidative Carbon-Carbon Bond Formation with Palladium Complexes: A Computational Mechanistic Study. Journal of the American Chemical Society 2018, 140 (11), 3929–3939. https://doi.org/10.1021/jacs.7b11701
UR  - https://hdl.handle.net/21.15107/rcub_cherry_3310
ER  - 

@misc{
author = "Peng, Qian and Wang, Zengwei and Zarić, Snežana D. and Brothers, Edward N. and Hall, Michael B.",
year = "2018",
publisher = "Amer Chemical Soc, Washington",
journal = "Journal of the American Chemical Society",
title = "Supplementary data for the article: Peng, Q.; Wang, Z.; Zarić, S. D.; Brothers, E. N.; Hall, M. B. Unraveling the Role of a Flexible Tetradentate Ligand in the Aerobic Oxidative Carbon-Carbon Bond Formation with Palladium Complexes: A Computational Mechanistic Study. Journal of the American Chemical Society 2018, 140 (11), 3929–3939. https://doi.org/10.1021/jacs.7b11701",
url = "https://hdl.handle.net/21.15107/rcub_cherry_3310"
}

Peng, Q., Wang, Z., Zarić, S. D., Brothers, E. N.,& Hall, M. B.. (2018). Supplementary data for the article: Peng, Q.; Wang, Z.; Zarić, S. D.; Brothers, E. N.; Hall, M. B. Unraveling the Role of a Flexible Tetradentate Ligand in the Aerobic Oxidative Carbon-Carbon Bond Formation with Palladium Complexes: A Computational Mechanistic Study. Journal of the American Chemical Society 2018, 140 (11), 3929–3939. https://doi.org/10.1021/jacs.7b11701. in Journal of the American Chemical Society
Amer Chemical Soc, Washington..
https://hdl.handle.net/21.15107/rcub_cherry_3310

Peng Q, Wang Z, Zarić SD, Brothers EN, Hall MB. Supplementary data for the article: Peng, Q.; Wang, Z.; Zarić, S. D.; Brothers, E. N.; Hall, M. B. Unraveling the Role of a Flexible Tetradentate Ligand in the Aerobic Oxidative Carbon-Carbon Bond Formation with Palladium Complexes: A Computational Mechanistic Study. Journal of the American Chemical Society 2018, 140 (11), 3929–3939. https://doi.org/10.1021/jacs.7b11701. in Journal of the American Chemical Society. 2018;.
https://hdl.handle.net/21.15107/rcub_cherry_3310 .

Peng, Qian, Wang, Zengwei, Zarić, Snežana D., Brothers, Edward N., Hall, Michael B., "Supplementary data for the article: Peng, Q.; Wang, Z.; Zarić, S. D.; Brothers, E. N.; Hall, M. B. Unraveling the Role of a Flexible Tetradentate Ligand in the Aerobic Oxidative Carbon-Carbon Bond Formation with Palladium Complexes: A Computational Mechanistic Study. Journal of the American Chemical Society 2018, 140 (11), 3929–3939. https://doi.org/10.1021/jacs.7b11701" in Journal of the American Chemical Society (2018),
https://hdl.handle.net/21.15107/rcub_cherry_3310 .

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/123456789/3311
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 . .

TY  - JOUR
AU  - Guan, Jia
AU  - Wriglesworth, Alisdair
AU  - Sun, Xue Zhong
AU  - Brothers, Edward N.
AU  - Zarić, Snežana D.
AU  - Evans, Meagan E.
AU  - Jones, William D.
AU  - Towrie, Michael
AU  - Hall, Michael B.
AU  - George, Michael W.
PY  - 2018
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/2091
AB  - Carbon-hydrogen bond activation of alkanes by Tp'Rh(CNR) (Tp' = Tp = trispyrazolylborate or Tp* = tris(3,5- dimethylpyrazolyl)borate) were followed by time-resolved infrared spectroscopy (TRIR) in the upsilon(CNR) and upsilon(B-H) spectral regions on Tp*Rh(CNCH2CMe3), and their reaction mechanisms were modeled by density functional theory (DFT) on TpRh(CNMe). The major intermediate species were: kappa(3)-eta(1)-alkane complex (1); kappa(2)-kappa(2)-alkane complex (2); and kappa(3)-alkyl hydride (3). Calculations predict that the barrier between 1 and 2 arises from a triplet-singlet crossing and intermediate 2 proceeds over the rate-determining C-H activation barrier to give the final product 3. The activation lifetimes measured for the Tp*Rh(CNR) and Tp*Rh(CO) fragments with n-heptane and four cycloalkanes (C5H10, C6H12, C7H14, and C8H16) increase with alkanes size and show a dramatic increase between C6H12 and C7H14. A similar step-like behavior was observed previously with CpRh(CO) and Cp*Rh(CO) fragments and is attributed to the wider difference in C-H bonds that appear at C7H14. However, Tp'Rh(CNR) and Tp'Rh(CO) fragments have much longer absolute lifetimes compared to those of CpRh(CO) and Cp*Rh(CO) fragments, because the reduced electron density in dechelated kappa(2)-eta(2)-alkane Tp' complexes stabilizes the d(8) Rh(I) in a square-planar geometry and weakens the metal's ability for oxidative addition of the C-H bond. Further, the Tp'Rh(CNR) fragment has significantly slower rates of C-H activation in comparison to the Tp'Rh(CO) fragment for the larger cycloalkanes, because the steric bulk of the neopentyl isocyanide ligand hinders the rechelation in kappa(2)-Tp'Rh(CNR)(cycloalkane) species and results in the C-H activation without the assistance of the rechelation.
PB  - Amer Chemical Soc, Washington
T2  - Journal of the American Chemical Society
T1  - Probing the Carbon-Hydrogen Activation of Alkanes Following Photolysis of Tp'Rh(CNR)(carbodiimide): A Computational and Time Resolved Infrared Spectroscopic Study
VL  - 140
IS  - 5
SP  - 1842
EP  - 1854
DO  - 10.1021/jacs.7b12152
ER  - 

@article{
author = "Guan, Jia and Wriglesworth, Alisdair and Sun, Xue Zhong and Brothers, Edward N. and Zarić, Snežana D. and Evans, Meagan E. and Jones, William D. and Towrie, Michael and Hall, Michael B. and George, Michael W.",
year = "2018",
abstract = "Carbon-hydrogen bond activation of alkanes by Tp'Rh(CNR) (Tp' = Tp = trispyrazolylborate or Tp* = tris(3,5- dimethylpyrazolyl)borate) were followed by time-resolved infrared spectroscopy (TRIR) in the upsilon(CNR) and upsilon(B-H) spectral regions on Tp*Rh(CNCH2CMe3), and their reaction mechanisms were modeled by density functional theory (DFT) on TpRh(CNMe). The major intermediate species were: kappa(3)-eta(1)-alkane complex (1); kappa(2)-kappa(2)-alkane complex (2); and kappa(3)-alkyl hydride (3). Calculations predict that the barrier between 1 and 2 arises from a triplet-singlet crossing and intermediate 2 proceeds over the rate-determining C-H activation barrier to give the final product 3. The activation lifetimes measured for the Tp*Rh(CNR) and Tp*Rh(CO) fragments with n-heptane and four cycloalkanes (C5H10, C6H12, C7H14, and C8H16) increase with alkanes size and show a dramatic increase between C6H12 and C7H14. A similar step-like behavior was observed previously with CpRh(CO) and Cp*Rh(CO) fragments and is attributed to the wider difference in C-H bonds that appear at C7H14. However, Tp'Rh(CNR) and Tp'Rh(CO) fragments have much longer absolute lifetimes compared to those of CpRh(CO) and Cp*Rh(CO) fragments, because the reduced electron density in dechelated kappa(2)-eta(2)-alkane Tp' complexes stabilizes the d(8) Rh(I) in a square-planar geometry and weakens the metal's ability for oxidative addition of the C-H bond. Further, the Tp'Rh(CNR) fragment has significantly slower rates of C-H activation in comparison to the Tp'Rh(CO) fragment for the larger cycloalkanes, because the steric bulk of the neopentyl isocyanide ligand hinders the rechelation in kappa(2)-Tp'Rh(CNR)(cycloalkane) species and results in the C-H activation without the assistance of the rechelation.",
publisher = "Amer Chemical Soc, Washington",
journal = "Journal of the American Chemical Society",
title = "Probing the Carbon-Hydrogen Activation of Alkanes Following Photolysis of Tp'Rh(CNR)(carbodiimide): A Computational and Time Resolved Infrared Spectroscopic Study",
volume = "140",
number = "5",
pages = "1842-1854",
doi = "10.1021/jacs.7b12152"
}

Guan, J., Wriglesworth, A., Sun, X. Z., Brothers, E. N., Zarić, S. D., Evans, M. E., Jones, W. D., Towrie, M., Hall, M. B.,& George, M. W.. (2018). Probing the Carbon-Hydrogen Activation of Alkanes Following Photolysis of Tp'Rh(CNR)(carbodiimide): A Computational and Time Resolved Infrared Spectroscopic Study. in Journal of the American Chemical Society
Amer Chemical Soc, Washington., 140(5), 1842-1854.
https://doi.org/10.1021/jacs.7b12152

Guan J, Wriglesworth A, Sun XZ, Brothers EN, Zarić SD, Evans ME, Jones WD, Towrie M, Hall MB, George MW. Probing the Carbon-Hydrogen Activation of Alkanes Following Photolysis of Tp'Rh(CNR)(carbodiimide): A Computational and Time Resolved Infrared Spectroscopic Study. in Journal of the American Chemical Society. 2018;140(5):1842-1854.
doi:10.1021/jacs.7b12152 .

Guan, Jia, Wriglesworth, Alisdair, Sun, Xue Zhong, Brothers, Edward N., Zarić, Snežana D., Evans, Meagan E., Jones, William D., Towrie, Michael, Hall, Michael B., George, Michael W., "Probing the Carbon-Hydrogen Activation of Alkanes Following Photolysis of Tp'Rh(CNR)(carbodiimide): A Computational and Time Resolved Infrared Spectroscopic Study" in Journal of the American Chemical Society, 140, no. 5 (2018):1842-1854,
https://doi.org/10.1021/jacs.7b12152 . .

TY  - JOUR
AU  - Keith, Jason M.
AU  - Tomić, Zoran D.
AU  - Zarić, Snežana D.
AU  - Hall, Michael B.
PY  - 2010
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/1087
AB  - Catalytic oxygen atom transfer (OAT), which frequently employs molybdenum oxo species, is an important reaction for both nature and industry. The mechanistic details of oxygen atom transfer from Tp(R)MoO(2)(XPh) to PMe(3) were investigated for R = 3-iPr and 3-Me and X=O and S by density functional theory (DFT) calculations of the enthalpies, free energy with solvent corrections, and natural bond orbital (NBO) analysis. The mechanism for both systems proceeds via rate-determining attack of PMe(3) to form a stable intermediate with a bound OPMe(3) ligand. From this intermediate the reaction proceeds through a substitution involving loss of OPMe(3) and coordination of a single CH(3)CN solvent molecule. The solvent corrected free energy barriers of the rate-determining OAT step for the O and S systems were found to be energetically more favorable for the S systems by 6.2 and 2.2 kcal/mol (for the R=3-iPr and 3-Me, respectively). This lower energy barrier is the result of better stabilization by the SPh ligand of the Mo(IV) products and the transition states, which are the unexpectedly later and more product-like. Additional examination of the NBO analysis emphasizes the role of the local acidity of the Mo and by extension the character of the ligands. The decreased electronegativity and softer character of the S atom result in an increased covalent character in the Mo-X bond which leads to the stabilization of a later (and lower energy) transition state and the corresponding product of the S system relative to O system. (C) 2010 Elsevier B.V. All rights reserved.
PB  - Elsevier Science Bv, Amsterdam
T2  - Journal of Molecular Catalysis. A: Chemical
T1  - Oxygen atom transfer catalysis: Ligand effects on the key reaction barrier in molybdenum (VI) dioxo systems
VL  - 324
IS  - 1-2
SP  - 15
EP  - 23
DO  - 10.1016/j.molcata.2010.02.027
ER  - 

@article{
author = "Keith, Jason M. and Tomić, Zoran D. and Zarić, Snežana D. and Hall, Michael B.",
year = "2010",
abstract = "Catalytic oxygen atom transfer (OAT), which frequently employs molybdenum oxo species, is an important reaction for both nature and industry. The mechanistic details of oxygen atom transfer from Tp(R)MoO(2)(XPh) to PMe(3) were investigated for R = 3-iPr and 3-Me and X=O and S by density functional theory (DFT) calculations of the enthalpies, free energy with solvent corrections, and natural bond orbital (NBO) analysis. The mechanism for both systems proceeds via rate-determining attack of PMe(3) to form a stable intermediate with a bound OPMe(3) ligand. From this intermediate the reaction proceeds through a substitution involving loss of OPMe(3) and coordination of a single CH(3)CN solvent molecule. The solvent corrected free energy barriers of the rate-determining OAT step for the O and S systems were found to be energetically more favorable for the S systems by 6.2 and 2.2 kcal/mol (for the R=3-iPr and 3-Me, respectively). This lower energy barrier is the result of better stabilization by the SPh ligand of the Mo(IV) products and the transition states, which are the unexpectedly later and more product-like. Additional examination of the NBO analysis emphasizes the role of the local acidity of the Mo and by extension the character of the ligands. The decreased electronegativity and softer character of the S atom result in an increased covalent character in the Mo-X bond which leads to the stabilization of a later (and lower energy) transition state and the corresponding product of the S system relative to O system. (C) 2010 Elsevier B.V. All rights reserved.",
publisher = "Elsevier Science Bv, Amsterdam",
journal = "Journal of Molecular Catalysis. A: Chemical",
title = "Oxygen atom transfer catalysis: Ligand effects on the key reaction barrier in molybdenum (VI) dioxo systems",
volume = "324",
number = "1-2",
pages = "15-23",
doi = "10.1016/j.molcata.2010.02.027"
}

Keith, J. M., Tomić, Z. D., Zarić, S. D.,& Hall, M. B.. (2010). Oxygen atom transfer catalysis: Ligand effects on the key reaction barrier in molybdenum (VI) dioxo systems. in Journal of Molecular Catalysis. A: Chemical
Elsevier Science Bv, Amsterdam., 324(1-2), 15-23.
https://doi.org/10.1016/j.molcata.2010.02.027

Keith JM, Tomić ZD, Zarić SD, Hall MB. Oxygen atom transfer catalysis: Ligand effects on the key reaction barrier in molybdenum (VI) dioxo systems. in Journal of Molecular Catalysis. A: Chemical. 2010;324(1-2):15-23.
doi:10.1016/j.molcata.2010.02.027 .

Keith, Jason M., Tomić, Zoran D., Zarić, Snežana D., Hall, Michael B., "Oxygen atom transfer catalysis: Ligand effects on the key reaction barrier in molybdenum (VI) dioxo systems" in Journal of Molecular Catalysis. A: Chemical, 324, no. 1-2 (2010):15-23,
https://doi.org/10.1016/j.molcata.2010.02.027 . .

TY  - JOUR
AU  - George, Michael W.
AU  - Hall, Michael B.
AU  - Jina, Omar S.
AU  - Portius, Peter
AU  - Sun, Xue-Zhong
AU  - Towrie, Michael
AU  - Wu, Hong
AU  - Yang, Xinzheng
AU  - Zarić, Snežana D.
PY  - 2010
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/1136
AB  - Fast time-resolved infrared spectroscopic measurements have allowed precise determination of the rates of activation of alkanes by Cp'Rh(CO) (Cp' = eta(5)-C5H5 or eta(5)-C5Me5). We have monitored the kinetics of C-H activation in solution at room temperature and determined how the change in rate of oxidative cleavage varies from methane to decane. The lifetime of CpRh(CO)(alkane) shows a nearly linear behavior with respect to the length of the alkane chain, whereas the related Cp*Rh(CO)(alkane) has clear oscillatory behavior upon changing the alkane. Coupled cluster and density functional theory calculations on these complexes, transition states, and intermediates provide the insight into the mechanism and barriers in order to develop a kinetic simulation of the experimental results. The observed behavior is a subtle interplay between the rates of activation and migration. Unexpectedly, the calculations predict that the most rapid process in these Cp'Rh (CO)(alkane) systems is the 1,3-migration along the alkane chain. The linear behavior in the observed lifetime of CpRh(CO)(alkane) results from a mechanism in which the next most rapid process is the activation of primary C-H bonds (-CH3 groups), while the third key step in this system is 1,2-migration with a slightly slower rate. The oscillatory behavior in the lifetime of Cp*Rh(CO)(alkane) with respect to the alkane's chain length follows from subtle interplay between more rapid migrations and less rapid primary C-H activation, with respect to CpRh(CO)(alkane), especially when the CH3 group is near a gauche turn. This interplay results in the activation being controlled by the percentage of alkane conformers.
PB  - Natl Acad Sciences, Washington
T2  - Proceedings of the National Academy of Sciences of the United States
T1  - Understanding the factors affecting the activation of alkane by Cp ' Rh(CO)(2) (Cp ' = Cp or Cp*)
VL  - 107
IS  - 47
SP  - 20178
EP  - 20183
DO  - 10.1073/pnas.1001249107
ER  - 

@article{
author = "George, Michael W. and Hall, Michael B. and Jina, Omar S. and Portius, Peter and Sun, Xue-Zhong and Towrie, Michael and Wu, Hong and Yang, Xinzheng and Zarić, Snežana D.",
year = "2010",
abstract = "Fast time-resolved infrared spectroscopic measurements have allowed precise determination of the rates of activation of alkanes by Cp'Rh(CO) (Cp' = eta(5)-C5H5 or eta(5)-C5Me5). We have monitored the kinetics of C-H activation in solution at room temperature and determined how the change in rate of oxidative cleavage varies from methane to decane. The lifetime of CpRh(CO)(alkane) shows a nearly linear behavior with respect to the length of the alkane chain, whereas the related Cp*Rh(CO)(alkane) has clear oscillatory behavior upon changing the alkane. Coupled cluster and density functional theory calculations on these complexes, transition states, and intermediates provide the insight into the mechanism and barriers in order to develop a kinetic simulation of the experimental results. The observed behavior is a subtle interplay between the rates of activation and migration. Unexpectedly, the calculations predict that the most rapid process in these Cp'Rh (CO)(alkane) systems is the 1,3-migration along the alkane chain. The linear behavior in the observed lifetime of CpRh(CO)(alkane) results from a mechanism in which the next most rapid process is the activation of primary C-H bonds (-CH3 groups), while the third key step in this system is 1,2-migration with a slightly slower rate. The oscillatory behavior in the lifetime of Cp*Rh(CO)(alkane) with respect to the alkane's chain length follows from subtle interplay between more rapid migrations and less rapid primary C-H activation, with respect to CpRh(CO)(alkane), especially when the CH3 group is near a gauche turn. This interplay results in the activation being controlled by the percentage of alkane conformers.",
publisher = "Natl Acad Sciences, Washington",
journal = "Proceedings of the National Academy of Sciences of the United States",
title = "Understanding the factors affecting the activation of alkane by Cp ' Rh(CO)(2) (Cp ' = Cp or Cp*)",
volume = "107",
number = "47",
pages = "20178-20183",
doi = "10.1073/pnas.1001249107"
}

George, M. W., Hall, M. B., Jina, O. S., Portius, P., Sun, X., Towrie, M., Wu, H., Yang, X.,& Zarić, S. D.. (2010). Understanding the factors affecting the activation of alkane by Cp ' Rh(CO)(2) (Cp ' = Cp or Cp*). in Proceedings of the National Academy of Sciences of the United States
Natl Acad Sciences, Washington., 107(47), 20178-20183.
https://doi.org/10.1073/pnas.1001249107

George MW, Hall MB, Jina OS, Portius P, Sun X, Towrie M, Wu H, Yang X, Zarić SD. Understanding the factors affecting the activation of alkane by Cp ' Rh(CO)(2) (Cp ' = Cp or Cp*). in Proceedings of the National Academy of Sciences of the United States. 2010;107(47):20178-20183.
doi:10.1073/pnas.1001249107 .

George, Michael W., Hall, Michael B., Jina, Omar S., Portius, Peter, Sun, Xue-Zhong, Towrie, Michael, Wu, Hong, Yang, Xinzheng, Zarić, Snežana D., "Understanding the factors affecting the activation of alkane by Cp ' Rh(CO)(2) (Cp ' = Cp or Cp*)" in Proceedings of the National Academy of Sciences of the United States, 107, no. 47 (2010):20178-20183,
https://doi.org/10.1073/pnas.1001249107 . .

TY  - CONF
AU  - Zarić, Snežana D.
AU  - Milčić, Miloš K.
AU  - Stevic, M.
AU  - Holclajtner-Antunović, Ivanka
AU  - Hall, Michael B.
PY  - 2006
UR  - https://cherry.chem.bg.ac.rs/handle/123456789/924
AB  - In this contribution, we used Fenske-Hall molecular orbital method, an approximate self-consistent-field (SCF) ab initio method that contains no-empirical parameters. We demonstrate for polyoxometalate anion, Lindqvist metal oxide cluster, W6O192-, that the non-empirical Fenske-Hall (FH) approach provides qualitative results that are quite similar to the more rigorous treatment given by density functional theory (DFT).
PB  - Vsp Bv-C/O Brill Acad Publ, Leiden
T1  - Fenske-Hall calculations on polyoxometalate anion
SP  - 607
UR  - https://hdl.handle.net/21.15107/rcub_cherry_924
ER  - 

@conference{
author = "Zarić, Snežana D. and Milčić, Miloš K. and Stevic, M. and Holclajtner-Antunović, Ivanka and Hall, Michael B.",
year = "2006",
abstract = "In this contribution, we used Fenske-Hall molecular orbital method, an approximate self-consistent-field (SCF) ab initio method that contains no-empirical parameters. We demonstrate for polyoxometalate anion, Lindqvist metal oxide cluster, W6O192-, that the non-empirical Fenske-Hall (FH) approach provides qualitative results that are quite similar to the more rigorous treatment given by density functional theory (DFT).",
publisher = "Vsp Bv-C/O Brill Acad Publ, Leiden",
title = "Fenske-Hall calculations on polyoxometalate anion",
pages = "607",
url = "https://hdl.handle.net/21.15107/rcub_cherry_924"
}

Zarić, S. D., Milčić, M. K., Stevic, M., Holclajtner-Antunović, I.,& Hall, M. B.. (2006). Fenske-Hall calculations on polyoxometalate anion. 
Vsp Bv-C/O Brill Acad Publ, Leiden., 607.
https://hdl.handle.net/21.15107/rcub_cherry_924

Zarić SD, Milčić MK, Stevic M, Holclajtner-Antunović I, Hall MB. Fenske-Hall calculations on polyoxometalate anion. 2006;:607.
https://hdl.handle.net/21.15107/rcub_cherry_924 .

Zarić, Snežana D., Milčić, Miloš K., Stevic, M., Holclajtner-Antunović, Ivanka, Hall, Michael B., "Fenske-Hall calculations on polyoxometalate anion" (2006):607,
https://hdl.handle.net/21.15107/rcub_cherry_924 .