Characterization of Carbenes via Hydrogenation Energies, Stability, and Reactivity: What's in a Name?

Vasiliu, Monica; Peterson, Kirk A.; Arduengo, Anthony J.; Dixon, David A.

doi:10.1002/chem.201703539

Title: Characterization of Carbenes via Hydrogenation Energies, Stability, and Reactivity: What's in a Name?

Journal Article · Thu Nov 16 00:00:00 EST 2017 · Chemistry - A European Journal

DOI:https://doi.org/10.1002/chem.201703539· OSTI ID:1409477

Vasiliu, Monica ^[1];

^[2]; Arduengo, Anthony J. ^[1];

^[1]

Department of Chemistry The University of Alabama, Shelby Hall Tuscaloosa Alabama 35487-0336 USA
Department of Chemistry Washington State University Pullman WA 99164-4630 USA

Abstract The hydrogenation energies and singlet–triplet (S–T) splittings at the G3MP2 level of theory have been calculated for a wide range of carbenes. The carbene, :CXY with different substituents (X, Y=H, CN, NC, F, Cl, OH, OCH ₃ , CH ₃ , CF ₃ , SiH ₃ , SiMe ₃ , phenyl, CH=O, PH ₂ , and NH ₂ ) at the carbenic carbon center, immidazole‐based carbenes, Bertrand's carbenes, and Seppelt's CF ₃ CSF ₃ were studied. The stable carbenes are singlets with large S–T splittings and with the least exothermic hydrogenation energies. The singlet ground state immidazole‐based carbenes are calculated to have the least exothermic hydrogenation energies (−15 to −30 kcal mol ⁻¹ ) and the largest S–T gaps. The singlet ground states of the Bertrand carbenes have more exothermic hydrogenation (ca. −67 kcal mol ⁻¹ ) energies and much smaller S–T gaps. The more exothermic reaction energies arise due to the need to make the phosphorus planar in the carbene so that it can donate into the empty p‐orbital at the carbene carbon center. The bending potential at the carbene carbon center in the Bertrand compounds is very flat with a large XC:Y angle. Seppelt's CF ₃ CSF ₃ appears to be energetically similar to the Bertrand system, probably due to the required adjustments for geometric distortions at the sulfur center.

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Sponsoring Organization:: USDOE

OSTI ID:: 1409477

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Vol. 23 Journal Issue: 69; ISSN 0947-6539

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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Cited by: 9 works

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References (54)

Gaussian-3 theory using reduced Mo/ller-Plesset order Curtiss, Larry A.; Redfern, Paul C.; Raghavachari, Krishnan The Journal of Chemical Physics, Vol. 110, Issue 10 https://doi.org/10.1063/1.478385	journal	March 1999
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
N-Heterocyclic Carbene-Phosphinidyne Transition Metal Complexes Doddi, Adinarayana; Bockfeld, Dirk; Bannenberg, Thomas Angewandte Chemie International Edition, Vol. 53, Issue 49 https://doi.org/10.1002/anie.201408354	journal	October 2014
Reliable Determination of Amidicity in Acyclic Amides and Lactams Glover, Stephen A.; Rosser, Adam A. The Journal of Organic Chemistry, Vol. 77, Issue 13 https://doi.org/10.1021/jo300347k	journal	June 2012
Electron Distribution in a Stable Carbene Arduengo, Anthony J.; Dias, H. V. Rasika; Dixon, David A. Journal of the American Chemical Society, Vol. 116, Issue 15 https://doi.org/10.1021/ja00094a040	journal	July 1994
A stable crystalline carbene Arduengo, Anthony J.; Harlow, Richard L.; Kline, Michael Journal of the American Chemical Society, Vol. 113, Issue 1 https://doi.org/10.1021/ja00001a054	journal	January 1991
1,3,4,5-Tetramethyl-2-methyleneimidazoline—an ylidic olefin Kuhn, Norbert; Bohnen, Hans; Kreutzberg, Jörg J. Chem. Soc., Chem. Commun., Issue 14 https://doi.org/10.1039/C39930001136	journal	January 1993
Molpro: a general-purpose quantum chemistry program package: Molpro Werner, Hans-Joachim; Knowles, Peter J.; Knizia, Gerald Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 2 https://doi.org/10.1002/wcms.82	journal	July 2011
Accurate Heats of Formation of the “Arduengo-Type” Carbene and Various Adducts Including H ₂ from ab Initio Molecular Orbital Theory Dixon, David A.; Arduengo, Anthony J. The Journal of Physical Chemistry A, Vol. 110, Issue 5 https://doi.org/10.1021/jp055527i	journal	February 2006
Electronic Structure of Stable Carbenes, Silylenes, and Germylenes Boehme, Christian; Frenking, Gernot Journal of the American Chemical Society, Vol. 118, Issue 8 https://doi.org/10.1021/ja9527075	journal	January 1996
PhenoFluor: Practical Synthesis, New Formulation, and Deoxyfluorination of Heteroaromatics Fujimoto, Teppei; Becker, Fabian; Ritter, Tobias Organic Process Research & Development, Vol. 18, Issue 8 https://doi.org/10.1021/op500121w	journal	July 2014
Ein stabiles Tetraazafulvalen Andrew Taton, T.; Chen, Peter Angewandte Chemie, Vol. 108, Issue 9 https://doi.org/10.1002/ange.19961080926	journal	May 1996
Improved synthesis of N-heterocyclic olefins and evaluation of their donor strengths Powers, Kate; Hering-Junghans, Christian; McDonald, Robert Polyhedron, Vol. 108 https://doi.org/10.1016/j.poly.2015.07.070	journal	March 2016
Heats of Formation of Simple Perfluorinated Carbon Compounds Dixon, David A.; Feller, David; Sandrone, Giovanni The Journal of Physical Chemistry A, Vol. 103, Issue 24 https://doi.org/10.1021/jp990425b	journal	June 1999
Analogous .alpha.,.alpha.'-bis-carbenoid, triply bonded species: synthesis of a stable .lambda.3-phosphino carbene-.lambda.5-phosphaacetylene Igau, Alain.; Grutzmacher, Hansjorg.; Baceiredo, Antoine. Journal of the American Chemical Society, Vol. 110, Issue 19 https://doi.org/10.1021/ja00227a028	journal	September 1988
Chemical Shielding Tensor of a Carbene Arduengo, Anthony J.; Dixon, David A.; Kumashiro, Kristin K. Journal of the American Chemical Society, Vol. 116, Issue 14 https://doi.org/10.1021/ja00093a041	journal	July 1994
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen Dunning, Thom H. The Journal of Chemical Physics, Vol. 90, Issue 2 https://doi.org/10.1063/1.456153	journal	January 1989
Electronegativity: The density functional viewpoint Parr, Robert G.; Donnelly, Robert A.; Levy, Mel The Journal of Chemical Physics, Vol. 68, Issue 8 https://doi.org/10.1063/1.436185	journal	April 1978
Stable Carbenes Bourissou, Didier; Guerret, Olivier; Gabbaï, François P. Chemical Reviews, Vol. 100, Issue 1 https://doi.org/10.1021/cr940472u	journal	January 2000
The resonance energy of amides, the structure of aziridinone, and its relationship to other strained lactams Greenberg, Arthur; Chiu, Yeu-Yi; Johnson, Jeri L. Structural Chemistry, Vol. 2, Issue 2 https://doi.org/10.1007/BF00676622	journal	February 1991
Amidicity Change as a Significant Driving Force and Thermodynamic Selection Rule of Transamidation Reactions. A Synergy between Experiment and Theory Mucsi, Zoltán; Chass, Gregory A.; Csizmadia, Imre G. The Journal of Physical Chemistry B, Vol. 112, Issue 26 https://doi.org/10.1021/jp8023292	journal	July 2008
NBO 6.0 : Natural bond orbital analysis program Glendening, Eric D.; Landis, Clark R.; Weinhold, Frank Journal of Computational Chemistry, Vol. 34, Issue 16 https://doi.org/10.1002/jcc.23266	journal	March 2013
Calculation of negative electron affinity and aqueous anion hardness using Kohn–Sham HOMO and LUMO energies De Proft, Frank; Sablon, Nick; Tozer, David J. Faraday Discuss., Vol. 135 https://doi.org/10.1039/B605302P	journal	January 2007
Looking for Stable Carbenes: The Difficulty in Starting Anew Arduengo, Anthony J. Accounts of Chemical Research, Vol. 32, Issue 11 https://doi.org/10.1021/ar980126p	journal	November 1999
Further benchmarks of a composite, convergent, statistically calibrated coupled-cluster-based approach for thermochemical and spectroscopic studies Feller, David; Peterson, Kirk A.; Dixon, David A. Molecular Physics, Vol. 110, Issue 19-20 https://doi.org/10.1080/00268976.2012.684897	journal	April 2012
A second order multiconfiguration SCF procedure with optimum convergence Werner, Hans‐Joachim; Knowles, Peter J. The Journal of Chemical Physics, Vol. 82, Issue 11 https://doi.org/10.1063/1.448627	journal	June 1985
Intercepting low oxidation state main group hydrides with a nucleophilic N-heterocyclic olefin Ibrahim Al-Rafia, S. M.; Malcolm, Adam C.; Liew, Sean K. Chemical Communications, Vol. 47, Issue 24 https://doi.org/10.1039/c1cc11737h	journal	January 2011
A Quantitative Scale for the Extent of Conjugation of the Amide Bond. Amidity Percentage as a Chemical Driving Force Mucsi, Zoltán; Tsai, Alex; Szori, Milan The Journal of Physical Chemistry A, Vol. 111, Issue 50 https://doi.org/10.1021/jp0759325	journal	December 2007
The complete active space SCF (CASSCF) method in a Newton–Raphson formulation with application to the HNO molecule Siegbahn, Per E. M.; Almlöf, Jan; Heiberg, Anders The Journal of Chemical Physics, Vol. 74, Issue 4 https://doi.org/10.1063/1.441359	journal	February 1981
Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint Reed, Alan E.; Curtiss, Larry A.; Weinhold, Frank Chemical Reviews, Vol. 88, Issue 6 https://doi.org/10.1021/cr00088a005	journal	September 1988
Optimization of Gaussian-type basis sets for local spin density functional calculations. Part I. Boron through neon, optimization technique and validation Godbout, Nathalie; Salahub, Dennis R.; Andzelm, Jan Canadian Journal of Chemistry, Vol. 70, Issue 2 https://doi.org/10.1139/v92-079	journal	February 1992
An efficient second-order MC SCF method for long configuration expansions Knowles, Peter J.; Werner, Hans-Joachim Chemical Physics Letters, Vol. 115, Issue 3 https://doi.org/10.1016/0009-2614(85)80025-7	journal	April 1985
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
Bond Energies in Models of the Schrock Metathesis Catalyst Vasiliu, Monica; Li, Shenggang; Arduengo, Anthony J. The Journal of Physical Chemistry C, Vol. 115, Issue 24 https://doi.org/10.1021/jp202668p	journal	May 2011
A complete active space SCF method (CASSCF) using a density matrix formulated super-CI approach Roos, Björn O.; Taylor, Peter R.; Sigbahn, Per E. M. Chemical Physics, Vol. 48, Issue 2 https://doi.org/10.1016/0301-0104(80)80045-0	journal	May 1980
Carbene-Based Lewis Pairs for Hydrogen Activation Runyon, Jason W.; Steinhof, Oliver; Dias, H. V. Rasika Australian Journal of Chemistry, Vol. 64, Issue 8 https://doi.org/10.1071/CH11246	journal	January 2011
Computation of the Hardness and the Problem of Negative Electron Affinities in Density Functional Theory Tozer, David J.; De Proft, Frank The Journal of Physical Chemistry A, Vol. 109, Issue 39 https://doi.org/10.1021/jp053504y	journal	October 2005
Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)] Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 78, Issue 7 https://doi.org/10.1103/PhysRevLett.78.1396	journal	February 1997
Conceptual Density Functional Theory Geerlings, P.; De Proft, F.; Langenaeker, W. Chemical Reviews, Vol. 103, Issue 5 https://doi.org/10.1021/cr990029p	journal	May 2003
Photoelectron Spectroscopy of a Carbene/Silylene/Germylene Series Arduengo, Anthony J.; Bock, Hans; Chen, Han Journal of the American Chemical Society, Vol. 116, Issue 15 https://doi.org/10.1021/ja00094a020	journal	July 1994
Stabilities of Carbenes: Independent Measures for Singlets and Triplets Gronert, Scott; Keeffe, James R.; More O’Ferrall, Rory A. Journal of the American Chemical Society, Vol. 133, Issue 10 https://doi.org/10.1021/ja1071493	journal	March 2011
Chemical accuracy in ab initio thermochemistry and spectroscopy: current strategies and future challenges Peterson, Kirk A.; Feller, David; Dixon, David A. Theoretical Chemistry Accounts, Vol. 131, Issue 1 https://doi.org/10.1007/s00214-011-1079-5	journal	January 2012
Absolute hardness: companion parameter to absolute electronegativity Parr, Robert G.; Pearson, Ralph G. Journal of the American Chemical Society, Vol. 105, Issue 26 https://doi.org/10.1021/ja00364a005	journal	December 1983
Density-Functional Theory of the Electronic Structure of Molecules Parr, Robert G.; Yang, Weitao Annual Review of Physical Chemistry, Vol. 46, Issue 1 https://doi.org/10.1146/annurev.pc.46.100195.003413	journal	October 1995
An Air Stable Carbene and Mixed Carbene “Dimers” Arduengo, Anthony J.; Davidson, Frederic; Dias, H. V. R. Journal of the American Chemical Society, Vol. 119, Issue 52 https://doi.org/10.1021/ja973241o	journal	December 1997
Electronic stabilization of nucleophilic carbenes Arduengo, Anthony J.; Dias, H. V. Rasika; Harlow, Richard L. Journal of the American Chemical Society, Vol. 114, Issue 14 https://doi.org/10.1021/ja00040a007	journal	July 1992
Absolute electronegativity and hardness correlated with molecular orbital theory Pearson, R. G. Proceedings of the National Academy of Sciences, Vol. 83, Issue 22 https://doi.org/10.1073/pnas.83.22.8440	journal	November 1986
A Brief Survey of Our Contribution to Stable Carbene Chemistry Martin, David; Melaimi, Mohand; Soleilhavoup, Michele Organometallics, Vol. 30, Issue 20 https://doi.org/10.1021/om200650x	journal	October 2011
A Stable Tetraazafulvalene Taton, T. Andrew; Chen, Peter Angewandte Chemie International Edition in English, Vol. 35, Issue 9 https://doi.org/10.1002/anie.199610111	journal	May 1996
N-Heterocyclic Carbene-Phosphinidyne Transition Metal Complexes Doddi, Adinarayana; Bockfeld, Dirk; Bannenberg, Thomas Angewandte Chemie, Vol. 126, Issue 49 https://doi.org/10.1002/ange.201408354	journal	October 2014
Über die Zuordnung von Wellenfunktionen und Eigenwerten zu den Einzelnen Elektronen Eines Atoms Koopmans, T. Physica, Vol. 1, Issue 1-6 https://doi.org/10.1016/S0031-8914(34)90011-2	journal	January 1934
Electronic structure of phosphine. Effect of basic set and correlation on the inversion barrier Marynick, Dennis S.; Dixon, David A. The Journal of Physical Chemistry, Vol. 86, Issue 6 https://doi.org/10.1021/j100395a015	journal	March 1982
A survey of factors contributing to accurate theoretical predictions of atomization energies and molecular structures Feller, David; Peterson, Kirk A.; Dixon, David A. The Journal of Chemical Physics, Vol. 129, Issue 20 https://doi.org/10.1063/1.3008061	journal	November 2008
Trifluoroethylidynesulfur Trifluoride, F3CCSF3 Pötter, Brigitte; Seppelt, Konrad Angewandte Chemie International Edition in English, Vol. 23, Issue 2 https://doi.org/10.1002/anie.198401501	journal	February 1984

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