Chiral‐at‐Molybdenum – A Computational Study on N‐Substituted cis‐MoO 2 (nacnac) 2
Abstract Cis‐MoO 2 (nacnac) 2 (nacnac=β‐diketiminate) can be a viable chiral‐at‐metal catalyst when its two β‐diketiminate (nacnac) ligands are N‐substituted to prevent Λ⇌Δ racemization. Even simple methyl groups raise the barriers for racemization significantly for the Bailar, Rây‐Dutt, Conte‐Hippl...
Published in: | European Journal of Inorganic Chemistry |
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Online Access: | http://dx.doi.org/10.1002/ejic.202300256 |
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crwiley:10.1002/ejic.202300256 2024-06-02T08:05:47+00:00 Chiral‐at‐Molybdenum – A Computational Study on N‐Substituted cis‐MoO 2 (nacnac) 2 Dhimba, George Muller, Alfred Lammertsma, Koop National Research Foundation 2023 http://dx.doi.org/10.1002/ejic.202300256 en eng Wiley http://creativecommons.org/licenses/by-nc/4.0/ European Journal of Inorganic Chemistry volume 26, issue 25 ISSN 1434-1948 1099-0682 journal-article 2023 crwiley https://doi.org/10.1002/ejic.202300256 2024-05-03T11:22:28Z Abstract Cis‐MoO 2 (nacnac) 2 (nacnac=β‐diketiminate) can be a viable chiral‐at‐metal catalyst when its two β‐diketiminate (nacnac) ligands are N‐substituted to prevent Λ⇌Δ racemization. Even simple methyl groups raise the barriers for racemization significantly for the Bailar, Rây‐Dutt, Conte‐Hippler, and Dhimba‐Muller‐Lammertsma (DML) twists to a respectable 28.5, 37.8, 30.5, and 25.1 kcal/mol, respectively, at ωB97X‐D/6‐311+G(2d,p) (LANL2DZ for Mo) including acetonitrile solvation. The lowest energy DML barrier increases to ΔG o =27.4 kcal/mol with N‐substituted t‐butyl groups. The nacnac ligands’ electronic and steric components to the racemization barriers are discussed. Article in Journal/Newspaper DML Wiley Online Library European Journal of Inorganic Chemistry 26 25 |
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Wiley Online Library |
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English |
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Abstract Cis‐MoO 2 (nacnac) 2 (nacnac=β‐diketiminate) can be a viable chiral‐at‐metal catalyst when its two β‐diketiminate (nacnac) ligands are N‐substituted to prevent Λ⇌Δ racemization. Even simple methyl groups raise the barriers for racemization significantly for the Bailar, Rây‐Dutt, Conte‐Hippler, and Dhimba‐Muller‐Lammertsma (DML) twists to a respectable 28.5, 37.8, 30.5, and 25.1 kcal/mol, respectively, at ωB97X‐D/6‐311+G(2d,p) (LANL2DZ for Mo) including acetonitrile solvation. The lowest energy DML barrier increases to ΔG o =27.4 kcal/mol with N‐substituted t‐butyl groups. The nacnac ligands’ electronic and steric components to the racemization barriers are discussed. |
author2 |
National Research Foundation |
format |
Article in Journal/Newspaper |
author |
Dhimba, George Muller, Alfred Lammertsma, Koop |
spellingShingle |
Dhimba, George Muller, Alfred Lammertsma, Koop Chiral‐at‐Molybdenum – A Computational Study on N‐Substituted cis‐MoO 2 (nacnac) 2 |
author_facet |
Dhimba, George Muller, Alfred Lammertsma, Koop |
author_sort |
Dhimba, George |
title |
Chiral‐at‐Molybdenum – A Computational Study on N‐Substituted cis‐MoO 2 (nacnac) 2 |
title_short |
Chiral‐at‐Molybdenum – A Computational Study on N‐Substituted cis‐MoO 2 (nacnac) 2 |
title_full |
Chiral‐at‐Molybdenum – A Computational Study on N‐Substituted cis‐MoO 2 (nacnac) 2 |
title_fullStr |
Chiral‐at‐Molybdenum – A Computational Study on N‐Substituted cis‐MoO 2 (nacnac) 2 |
title_full_unstemmed |
Chiral‐at‐Molybdenum – A Computational Study on N‐Substituted cis‐MoO 2 (nacnac) 2 |
title_sort |
chiral‐at‐molybdenum – a computational study on n‐substituted cis‐moo 2 (nacnac) 2 |
publisher |
Wiley |
publishDate |
2023 |
url |
http://dx.doi.org/10.1002/ejic.202300256 |
genre |
DML |
genre_facet |
DML |
op_source |
European Journal of Inorganic Chemistry volume 26, issue 25 ISSN 1434-1948 1099-0682 |
op_rights |
http://creativecommons.org/licenses/by-nc/4.0/ |
op_doi |
https://doi.org/10.1002/ejic.202300256 |
container_title |
European Journal of Inorganic Chemistry |
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26 |
container_issue |
25 |
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1800750674180308992 |