Data from: The influence of C(sp3)H-Selenium Interactions on the 77Se NMR Quantification of the π-Accepting Properties of Carbenes
dippAdCAAC5
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Description | All DFT calculations pertaining to CAAC5 with nitrogen bearing a diisopropylphenyl substituent, an adamantyl group containing the quaternary carbon alpha to carbene center, and two methyl groups on the backbone alpha to the nitrogen and its Selenium adduct. |
Scope And Content | Geometry optimization, frequency and population analyses for the free carbene were performed at the B3LYP/def2-TZVPP level of theory. Geometry optimization (from X-ray starting point), frequency and population analyses for the selenium adduct were performed at the BP86/def2-TZVPP level of theory. An additional population analysis based on Natural Bond Orbital theory was performed and included for the reader's convenience. The NMR_GIAO calculation on the Se adduct was done at the BP86/def2-TZVPP level of theory with a polarizable continuum model of chloroform assuming Bondi atomic radii. The .chk, .fchk, and .log files are included for all calculations. |
dippEt2CAAC5
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Description | All DFT calculations pertaining to CAAC5 with nitrogen bearing a diisopropylphenyl substituent, two ethyl groups at the quaternary carbon alpha to carbene center, and two methyl groups on the backbone alpha to the nitrogen. |
Scope And Content | Geometry optimization, frequency and population analyses for the free carbene were performed at the B3LYP/def2-TZVPP level of theory. The .chk, .fchk, and .log files are included for all calculations. |
AdMe2CAAC6_1Me
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Description | All DFT calculations pertaining to CAAC6 with nitrogen bearing an adamantyl substituent, two methyls at the quaternary carbon alpha to carbene center, and one methyl on the backbone alpha to the nitrogen and its Selenium adduct. |
Scope And Content | Geometry optimization, frequency and population analyses for the free carbene were performed at the B3LYP/def2-TZVPP level of theory. Geometry optimization (from X-ray starting point), frequency and population analyses for the selenium adduct were performed at the BP86/def2-TZVPP level of theory. The NMR_GIAO calculation on the Se adduct was done at the BP86/def2-TZVPP level of theory with a polarizable continuum model of acetone assuming Bondi atomic radii. The .chk, .fchk, and .log files are included for all calculations. |
CyMe2CAAC6_1Me
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Description | All DFT calculations pertaining to CAAC6 with nitrogen bearing a cyclohexyl substituent, two methyls at the quaternary carbon alpha to carbene center, and one methyl on the backbone alpha to the nitrogen and its Selenium adduct. |
Scope And Content | Geometry optimization, frequency and population analyses for the free carbene were performed at the B3LYP/def2-TZVPP level of theory. Geometry optimization (from X-ray starting point), frequency and population analyses for the selenium adduct were performed at the BP86/def2-TZVPP level of theory. The NMR_GIAO calculation on the Se adduct was done at the BP86/def2-TZVPP level of theory with a polarizable continuum model of acetone assuming Bondi atomic radii. The .chk, .fchk, and .log files are included for all calculations. |
dippAdCAAC6_2Me
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Description | All calculations pertaining to CAAC6 with nitrogen bearing a diisopropylphenyl substituent, an adamantyl group containing the quaternary carbon alpha to carbene center, and two methyl groups on the backbone alpha to the nitrogen and its Selenium adduct. |
Scope And Content | Geometry optimization, frequency and population analyses for the free carbene were performed at the B3LYP/def2-TZVPP level of theory. Geometry optimization (from X-ray starting point), frequency and population analyses for the selenium adduct were performed at the BP86/def2-TZVPP level of theory. An additional population analysis based on Natural Bond Orbital theory was performed and included for the reader's convenience. The NMR_GIAO calculation on the Se adduct was done at the BP86/def2-TZVPP level of theory with a polarizable continuum model of chloroform assuming Bondi atomic radii. The .chk, .fchk, and .log files are included for all calculations. |
dippEt2CAAC6_1Me
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Description | All DFT calculations pertaining to CAAC6 with nitrogen bearing a diisopropylphenyl substituent, two ethyl groups at the quaternary carbon alpha to carbene center, and one methyl on the backbone alpha to the nitrogen. |
Scope And Content | Geometry optimization, frequency and population analyses for the free carbene were performed at the B3LYP/def2-TZVPP level of theory. The .chk, .fchk, and .log files are included for all calculations. |
dippEt2CAAC6_2Me
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Description | All DFT calculations pertaining to CAAC6 with nitrogen bearing a diisopropylphenyl substituent, two ethyl groups at the quaternary carbon alpha to carbene center, and two methyl groups on the backbone alpha to the nitrogen. |
Scope And Content | Geometry optimization, frequency and population analyses for the free carbene were performed at the B3LYP/def2-TZVPP level of theory. The .chk, .fchk, and .log files are included for all calculations. |
iPrMe2CAAC6_1Me
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Description | All DFT calculations pertaining to CAAC6 with nitrogen bearing an isopropyl substituent, two methyls at the quaternary carbon alpha to carbene center, and one methyl on the backbone alpha to the nitrogen and its Selenium adduct. |
Scope And Content | Geometry optimization, frequency and population analyses for the free carbene were performed at the B3LYP/def2-TZVPP level of theory. Geometry optimization (from X-ray starting point), frequency and population analyses for the selenium adduct were performed at the BP86/def2-TZVPP level of theory. The NMR_GIAO calculations on the Se adducts were done at the BP86/def2-TZVPP level of theory with a polarizable continuum model of acetone assuming Bondi atomic radii. The "nonXray_rotamer" was created from the tBuMe2CAAC6_1Me adduct crystal structure after one methyl subtituent on the t-butyl was replaced with a hydrogen then optimized at the BP86/def2-TZVPP level of theory, with subsequent frequency and population analyses at the same level. NMR_GIAO calculation on the nonXray_rotamer was done at the BP86/def2-TZVPP level of theory with a polarizable continuum model of acetone assuming Bondi atomic radii. The .chk, .fchk, and .log files are included for all calculations. |
tBuMe2CAAC6_1Me
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Description | All DFT calculations pertaining to CAAC6 with nitrogen bearing a tert-butyl substituent, two methyls at the quaternary carbon alpha to carbene center, and one methyl on the backbone alpha to the nitrogen and its Selenium adduct. |
Scope And Content | Geometry optimization, frequency and population analyses for the free carbene were performed at the B3LYP/def2-TZVPP level of theory. Geometry optimization (from X-ray starting point), frequency and population analyses for the selenium adduct were performed at the BP86/def2-TZVPP level of theory. The NMR_GIAO calculation on the Se adducts was done at the BP86/def2-TZVPP level of theory with a polarizable continuum model of acetone assuming Bondi atomic radii. The .chk, .fchk, and .log files are included for all calculations. |
Me2Se
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Description | All calculations pertaining to Me2Se, which serves as an NMR 0 ppm standard. Comparison of isotropic shielding values between this and other Se compounds is comparable to what is done experimentally. |
Scope And Content | Geometry optimization, frequency and population analyses were performed at the BP86/def2-TZVPP level of theory. The NMR_GIAO calculations were done at the BP86/def2-TZVPP level of theory with a polarizable continuum model of both chloroform and acetone assuming Bondi atomic radii. The .chk, .fchk, and .log files are included for all calculations. |
- Collection
- Cite This Work
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Junor, Glen P.; Lorkowski, Jan; Weinstein, Cory M.; Jazzar, Rodolphe; Pietrazuk, Cezary; Bertrand, Guy (2020). Data from: The influence of C(sp3)H-Selenium Interactions on the 77Se NMR Quantification of the π-Accepting Properties of Carbenes. UC San Diego Library Digital Collections. Dataset. https://doi.org/10.6075/J06M357V
- Description
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Abstract: Selenium NMR has become a standard tool for scaling the π-accepting character of carbenes. Herein, we highlight that non-classical hydrogen bonding (NCHB), likely resulting from hyperconjugation, can play a significant role in the carbene-selenium 77Se NMR chemical shift, thus triggering a non-linear behaviour of the Se-Scale.
- Scope And Content
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Data pertaining to each carbene and corresponding selenium adduct can be downloaded. Downloadable files are organized by carbene and contain folders with data corresponding to free carbene and selenium adduct, as appropriate. Within the selenium adduct folder can be found files containing optimizations, frequencies, population analyses, and a folder with NMR_GIAO calculations, as necessary. Some folders have additional divisions if multiple geometries were considered. Free carbene folders include optimization, frequency, and population analysis. All .chk, .fchk, and .log files are provided for each calculation. Note, optimizations, frequencies, and population analyses are typically done in one job and are thus not separated into specific folders. Some items may have needed multiple jobs to complete, due to the nature of compute resources. Each subsequent job is included under the folder title "restart" in the appropriate folder, as necessary. All calculations are done with an ultrafine grid.
- Creation Date
- 2020-02 to 2020-07
- Date Issued
- 2020
- Authors
- Principal Investigator
- Co Principal Investigator
- Technical Details
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Gaussian 09, Revision D.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Wallingford CT, 2013.
- Funding
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Thanks are due to the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Catalysis Science Program, Award # DE-SC0009376 for financial support of this work. We are grateful to the Alfred P. Sloan Foundation's University Centre for Exemplary Mentoring (G.P.J.), the National Science Foundation Graduate Research Fellowship Program under Grant No DGE-1650112 (G.P.J.). We also acknowledge the Kościuszko Foundation, Iwanowska program No PPN/IWA/2018/1/00015 of Polish National Agency for Academic Exchange, the National Science Centre (Poland) project UMO2015/19/N/ST5/00538 and grant No POWR.03.02.00-00-I023/17 of the European union through the European Social Fund under the Operational Program Knowledge Education (J.L.), the Keck Foundation for computational resources, Dr. A. Mrse for his NMR expertise and Dr. M. Gembicky for his crystallographic expertise.
- Topics
Format
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- Language
- No linguistic content; Not applicable
- Identifier
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Identifier: Cesary Pietrazuk http://orcid.org/0000-0003-2413-0478
Identifier: Glen P. Junor https://orcid.org/0000-0002-6733-3577
Identifier: Guy Bertrand https://orcid.org/0000-0003-2623-2363
Identifier: Jan Lorkowski https://orcid.org/0000-0003-3436-1296
Identifier: Rodolphe Jazzar https://orcid.org/0000-0002-4156-7826
- Related Resource
- Junor, G. P., Lorkowski, J., Weinstein, C. M., Jazzar, R., Pietrazuk, C., Bertrand, G. The influence of C(sp3)H-Selenium Interactions on the 77Se NMR Quantification of the π-Accepting Properties of Carbenes. Angew. Chem. Int. Ed. 2020, 59, 22028 – 22033. https://doi.org/10.1002/anie.202010744
Primary associated publication
- License
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Creative Commons Attribution 4.0 International Public License
- Rights Holder
- UC Regents
- Copyright
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Under copyright (US)
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- Digital Object Made Available By
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Research Data Curation Program, UC San Diego, La Jolla, 92093-0175 (https://lib.ucsd.edu/rdcp)
- Last Modified
2024-01-26