N-Heterocyclic Carbene Analogues of Thiele and Chichibabin Hydrocarbons

Rottschäfer D, Ho NKT, Neumann B, Stammler H-G, van Gastel M, Andrada DM, Ghadwal R (2018)
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 57(20): 5838-5842.

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Zeitschriftenaufsatz | Veröffentlicht | Englisch
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Abstract / Bemerkung
Stable N-heterocyclic carbene analogues of Thiele and Chichibabin hydrocarbons, [(IPr)(C6H4)(IPr)] and [(IPr)(C6H4)(2)(IPr)] (4 and 5, respectively; IPr - C{N(2,6-iPr(2)C(6)H(3))}(2)CHCH), are reported. In a nickel-catalyzed double carbenylation of 1,4-Br2C6H4 and 4,4'-Br-2(C6H4)(2) with IPr (1), [(IPr)(C6H4)(IPr)](Br)(2) (2) and [(IPr)(C6H4)(2)(IPr)](Br)(2) (3) were generated, which respectively afforded 4 and 5 as crystalline solids upon reduction with KC8. Experimental and computational studies support the semiquinoidal nature of 5 with a small singlet-triplet energy gap Delta ES-T of 10.7 kcal mol(-1), whereas 4 features more quinoidal character with a rather large Delta ES-T of 25.6 kcal mol(-1). In view of the low Delta ES-T, 4 and 5 may be described as biradicaloids. Moreover, 5 has considerable (41%) diradical character.
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ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
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57
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20
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5838-5842
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Rottschäfer D, Ho NKT, Neumann B, et al. N-Heterocyclic Carbene Analogues of Thiele and Chichibabin Hydrocarbons. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION. 2018;57(20):5838-5842.
Rottschäfer, D., Ho, N. K. T., Neumann, B., Stammler, H. - G., van Gastel, M., Andrada, D. M., & Ghadwal, R. (2018). N-Heterocyclic Carbene Analogues of Thiele and Chichibabin Hydrocarbons. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 57(20), 5838-5842. doi:10.1002/anie.201713346
Rottschäfer, D., Ho, N. K. T., Neumann, B., Stammler, H. - G., van Gastel, M., Andrada, D. M., and Ghadwal, R. (2018). N-Heterocyclic Carbene Analogues of Thiele and Chichibabin Hydrocarbons. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 57, 5838-5842.
Rottschäfer, D., et al., 2018. N-Heterocyclic Carbene Analogues of Thiele and Chichibabin Hydrocarbons. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 57(20), p 5838-5842.
D. Rottschäfer, et al., “N-Heterocyclic Carbene Analogues of Thiele and Chichibabin Hydrocarbons”, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, vol. 57, 2018, pp. 5838-5842.
Rottschäfer, D., Ho, N.K.T., Neumann, B., Stammler, H.-G., van Gastel, M., Andrada, D.M., Ghadwal, R.: N-Heterocyclic Carbene Analogues of Thiele and Chichibabin Hydrocarbons. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION. 57, 5838-5842 (2018).
Rottschäfer, Dennis, Ho, Nga Kim T., Neumann, Beate, Stammler, Hans-Georg, van Gastel, Maurice, Andrada, Diego M., and Ghadwal, Rajendra. “N-Heterocyclic Carbene Analogues of Thiele and Chichibabin Hydrocarbons”. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 57.20 (2018): 5838-5842.

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