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C–H Bond Activation by the Excited Zinc Atom: Gas-Phase Formation of Methylzinc Hydride (HZnCH(3)) Based on Multireference Second-Order Perturbation Theory and Coupled Cluster Calculations

[Image: see text] The pioneering spectroscopic observations of the methylzinc hydride [HZnCH(3)(X(1)A(1))] molecule were reported previously by the Ziurys group [J. Am. Chem. Soc.2010, 132, 17186–17192], and the possible formation mechanisms were suggested therein, including those with the participa...

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Autor principal: Moc, Jerzy
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8459409/
https://www.ncbi.nlm.nih.gov/pubmed/34568705
http://dx.doi.org/10.1021/acsomega.1c04531
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author Moc, Jerzy
author_facet Moc, Jerzy
author_sort Moc, Jerzy
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description [Image: see text] The pioneering spectroscopic observations of the methylzinc hydride [HZnCH(3)(X(1)A(1))] molecule were reported previously by the Ziurys group [J. Am. Chem. Soc.2010, 132, 17186–17192], and the possible formation mechanisms were suggested therein, including those with the participation of excited zinc atoms in reaction with methane. Herein, the ground singlet state and the lowest excited triplet state potential energy surfaces of the Zn + CH(4) reaction have been explored using high-level electronic structure calculations with multireference second-order perturbation theory and coupled cluster singles and doubles with perturbative triples (CCSD(T)) methods in conjunction with all-electron basis sets (up to aug-cc-pV5Z) and scalar relativistic effects incorporated via the second-order Douglas–Kroll–Hess (DK) method. Based on the ab initio results, a plausible scenario for the formation of HZnCH(3)(X(1)A(1)) is proposed involving the activation of the C–H bond of methane by the lowest excited (3)P state atomic zinc. Calculations also highlight the importance of an agostic-like Zn···H–C interactions in the pre-activation complex and good agreement between the structure of the HZnCH(3)(X(1)A(1)) molecule predicted at the DK-CCSD(T)/aug-cc-pVQZ-DK level of theory and that derived from rotational spectroscopy, as well as the discrepancies between the ab initio and density functional theory predictions.
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spelling pubmed-84594092021-09-24 C–H Bond Activation by the Excited Zinc Atom: Gas-Phase Formation of Methylzinc Hydride (HZnCH(3)) Based on Multireference Second-Order Perturbation Theory and Coupled Cluster Calculations Moc, Jerzy ACS Omega [Image: see text] The pioneering spectroscopic observations of the methylzinc hydride [HZnCH(3)(X(1)A(1))] molecule were reported previously by the Ziurys group [J. Am. Chem. Soc.2010, 132, 17186–17192], and the possible formation mechanisms were suggested therein, including those with the participation of excited zinc atoms in reaction with methane. Herein, the ground singlet state and the lowest excited triplet state potential energy surfaces of the Zn + CH(4) reaction have been explored using high-level electronic structure calculations with multireference second-order perturbation theory and coupled cluster singles and doubles with perturbative triples (CCSD(T)) methods in conjunction with all-electron basis sets (up to aug-cc-pV5Z) and scalar relativistic effects incorporated via the second-order Douglas–Kroll–Hess (DK) method. Based on the ab initio results, a plausible scenario for the formation of HZnCH(3)(X(1)A(1)) is proposed involving the activation of the C–H bond of methane by the lowest excited (3)P state atomic zinc. Calculations also highlight the importance of an agostic-like Zn···H–C interactions in the pre-activation complex and good agreement between the structure of the HZnCH(3)(X(1)A(1)) molecule predicted at the DK-CCSD(T)/aug-cc-pVQZ-DK level of theory and that derived from rotational spectroscopy, as well as the discrepancies between the ab initio and density functional theory predictions. American Chemical Society 2021-09-06 /pmc/articles/PMC8459409/ /pubmed/34568705 http://dx.doi.org/10.1021/acsomega.1c04531 Text en © 2021 The Author. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Moc, Jerzy
C–H Bond Activation by the Excited Zinc Atom: Gas-Phase Formation of Methylzinc Hydride (HZnCH(3)) Based on Multireference Second-Order Perturbation Theory and Coupled Cluster Calculations
title C–H Bond Activation by the Excited Zinc Atom: Gas-Phase Formation of Methylzinc Hydride (HZnCH(3)) Based on Multireference Second-Order Perturbation Theory and Coupled Cluster Calculations
title_full C–H Bond Activation by the Excited Zinc Atom: Gas-Phase Formation of Methylzinc Hydride (HZnCH(3)) Based on Multireference Second-Order Perturbation Theory and Coupled Cluster Calculations
title_fullStr C–H Bond Activation by the Excited Zinc Atom: Gas-Phase Formation of Methylzinc Hydride (HZnCH(3)) Based on Multireference Second-Order Perturbation Theory and Coupled Cluster Calculations
title_full_unstemmed C–H Bond Activation by the Excited Zinc Atom: Gas-Phase Formation of Methylzinc Hydride (HZnCH(3)) Based on Multireference Second-Order Perturbation Theory and Coupled Cluster Calculations
title_short C–H Bond Activation by the Excited Zinc Atom: Gas-Phase Formation of Methylzinc Hydride (HZnCH(3)) Based on Multireference Second-Order Perturbation Theory and Coupled Cluster Calculations
title_sort c–h bond activation by the excited zinc atom: gas-phase formation of methylzinc hydride (hznch(3)) based on multireference second-order perturbation theory and coupled cluster calculations
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8459409/
https://www.ncbi.nlm.nih.gov/pubmed/34568705
http://dx.doi.org/10.1021/acsomega.1c04531
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