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Theory predicts triplet ground-state carbene containing the N-heterocyclic carbenic unit

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Abstract

A theoretical study of singlet- and triplet-state cyclic vinylidenes was performed using the B3LYP, B3PW91, CCSD, CCSD(T), QCISD, and QCISD(T) methods at the 6-311G(d), 6-311++G(d,p), 6-311++G(df,pd), 6-311++G(2df,2pd), and 6-311++G(3df,3pd) basis sets. Fifty-eight vinylidenes, featuring the N-heterocyclic carbenic (NHC) unit, were chosen as the model molecules for this study. The computations demonstrate that fifty-one cyclic vinylidenes are predicted to have a triplet ground state with a singlet and triplet splitting energy of approximately −0.11 to −20 and −1.8 to −21 kcal/mol, for the B3LYP/6-311++G(d,p) and B3PW91/6-311++G(df,pd) levels of theory. Our theoretical findings suggest that it is the π-electron-rich ability of the NHC ring that makes cyclic vinylidene preferably adopt the triplet ground state. A valence electron model was used to explain the computational results. The theoretical observations strongly suggest that besides the traditional fact that the carbenic center is attached by two sterically bulky substituents, the use of an NHC skeleton can significantly increase the probability of producing a vinylidene that has a triplet ground state.

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Notes

  1. All computations were done using the Gaussian 03 package. For details, see the Supporting Information.

  2. We thank one reviewer for this suggestion.

  3. For instance, in the case of NHCHCHNH)C=C:, using the NBO analysis, one can obtain two π C=C → σ NC* interactions, each having 33.5 kcal/mol stabilizing energy for the triplet state. Also, there are two σ NC → π C=C* interactions, each stabilizing the triplet state by 14.2 kcal/mol. For details, see http://www.chem.wisc.edu/~nbo5.

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Acknowledgments

The authors are grateful to the National Center for High-Performance Computing of Taiwan for generous amounts of computing time. They also thank the National Science Council of Taiwan for the financial support. We express our gratitude to the referees for their valuable comments.

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Authors and Affiliations

  1. Department of Applied Chemistry, National Chiayi University, Chiayi, 60004, Taiwan

    Ming-Der Su & Chung-Ching Chuang

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  1. Ming-Der Su
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  2. Chung-Ching Chuang
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Correspondence to Ming-Der Su.

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Su, MD., Chuang, CC. Theory predicts triplet ground-state carbene containing the N-heterocyclic carbenic unit. Theor Chem Acc 132, 1360 (2013). https://doi.org/10.1007/s00214-013-1360-x

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