Kekule diradicaloids derived from a classical N-heterocyclic carbene

Rottschäfer D, Neumann B, Stammler H-G, Andrada DM, Ghadwal R (2018)
CHEMICAL SCIENCE 9(22): 4970-4976.

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Abstract / Bemerkung
The direct double carbenylation of 1,4-diiodobenzene and 4,4'-dibromobiphenyl with a classical N-heterocyclic carbene, SIPr (1) (SIPr = : C{N(2,6-iPr(2)C(6)H(3))}(2)CH2CH2), by means of nickel catalysis gives rise to 1,3-imidazolinium salts [(SIPr)(C6H4)(SIPr)](I)(2) (2) and [(SIPr)(C6H4)(2)(SIPr)](Br)(2) (3) as off-white solids. Two-electron reduction of 2 and 3 with KC8 cleanly yields Kekule diradicaloid compounds [(SIPr)(C6H4)(SIPr)] (4) and [(SIPr)(C6H4)(2)(SIPr)] (5), respectively, as crystalline solids. Structural parameters and DFT as well as CASSCF calculations suggest the closed-shell singlet ground state for 4 and 5. Calculations reveal a very low singlet-triplet energy gap Delta ES-T for 5 (10.7 kcal mol(-1)), while Delta ES-T for 4 (29.1 kcal mol(-1)) is rather large.
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CHEMICAL SCIENCE
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9
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22
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4970-4976
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Rottschäfer D, Neumann B, Stammler H-G, Andrada DM, Ghadwal R. Kekule diradicaloids derived from a classical N-heterocyclic carbene. CHEMICAL SCIENCE. 2018;9(22):4970-4976.
Rottschäfer, D., Neumann, B., Stammler, H. - G., Andrada, D. M., & Ghadwal, R. (2018). Kekule diradicaloids derived from a classical N-heterocyclic carbene. CHEMICAL SCIENCE, 9(22), 4970-4976. doi:10.1039/c8sc01209a
Rottschäfer, D., Neumann, B., Stammler, H. - G., Andrada, D. M., and Ghadwal, R. (2018). Kekule diradicaloids derived from a classical N-heterocyclic carbene. CHEMICAL SCIENCE 9, 4970-4976.
Rottschäfer, D., et al., 2018. Kekule diradicaloids derived from a classical N-heterocyclic carbene. CHEMICAL SCIENCE, 9(22), p 4970-4976.
D. Rottschäfer, et al., “Kekule diradicaloids derived from a classical N-heterocyclic carbene”, CHEMICAL SCIENCE, vol. 9, 2018, pp. 4970-4976.
Rottschäfer, D., Neumann, B., Stammler, H.-G., Andrada, D.M., Ghadwal, R.: Kekule diradicaloids derived from a classical N-heterocyclic carbene. CHEMICAL SCIENCE. 9, 4970-4976 (2018).
Rottschäfer, Dennis, Neumann, Beate, Stammler, Hans-Georg, Andrada, Diego M., and Ghadwal, Rajendra. “Kekule diradicaloids derived from a classical N-heterocyclic carbene”. CHEMICAL SCIENCE 9.22 (2018): 4970-4976.

2 Zitationen in Europe PMC

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Carbene derived diradicaloids - building blocks for singlet fission?
Messelberger J, Grünwald A, Pinter P, Hansmann MM, Munz D., Chem Sci 9(28), 2018
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