التفاصيل البيبلوغرافية
| العنوان: |
Small, Electron-Donating Substituents Give CO 2 Activation by Permethylpentalene Zirconium Amido Complexes the Upper Hand: A DFT Study of Distortion and Interaction. |
| المؤلفون: |
Chabeda D; Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States., Kelly HR; Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States.; Yale Energy Sciences Institute, Yale University, West Haven, Connecticut 06516, United States., Holland PL; Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States., Batista VS; Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States.; Yale Energy Sciences Institute, Yale University, West Haven, Connecticut 06516, United States. |
| المصدر: |
Inorganic chemistry [Inorg Chem] 2023 Feb 20; Vol. 62 (7), pp. 3000-3006. Date of Electronic Publication: 2023 Feb 08. |
| نوع المنشور: |
Journal Article |
| اللغة: |
English |
| بيانات الدورية: |
Publisher: American Chemical Society Country of Publication: United States NLM ID: 0366543 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1520-510X (Electronic) Linking ISSN: 00201669 NLM ISO Abbreviation: Inorg Chem Subsets: PubMed not MEDLINE; MEDLINE |
| أسماء مطبوعة: |
Original Publication: [Easton, Pa.] American Chemical Society. |
| مستخلص: |
An insight into factors controlling CO 2 activation is necessary to develop molecular systems that utilize CO 2 as a chemical feedstock. Two permethylpentalene zirconium cyclopentadienyl (mono)amido complexes, Pn*ZrCp(NR 2 ), were previously assessed for CO 2 activation, and a strong dependence on the amido substituent was observed. The R = Me analogue reacted rapidly and quantitatively at room temperature to form the carbamato complex, while the R = Ph species was inert. Here, we investigate the origin of this reactivity difference using DFT and the distortion-interaction model to characterize steric and electronic contributions to the activation barrier. We find that the barrier for CO 2 insertion with R = Me (19.1 kcal/mol) is lower than with R = Ph (36.6 kcal/mol), explaining the inertness of the Ph-substituted analogue. The distortion energy trend follows the steric bulk of the amido substituents, and the bulkier Ph-substituted complex has a consistently higher distortion energy along its potential energy surface than that of the Me-substituted complex. The interaction energy trend follows the electronics, and a more electron-donating Me-substituted complex shows a consistently lower interaction energy. The balance of these effects at the corresponding TS gives a reduced activation barrier. Small, electron-donating substituents therefore facilitate CO 2 activation in these complexes. |
| تواريخ الأحداث: |
Date Created: 20230208 Date Completed: 20230222 Latest Revision: 20230222 |
| رمز التحديث: |
20230222 |
| DOI: |
10.1021/acs.inorgchem.2c03533 |
| PMID: |
36752721 |
| قاعدة البيانات: |
MEDLINE |
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