Kekul diradicaloids derived from a classical N-heterocyclic carbeneElectronic supplementary information (ESI) available. CCDC 18265671826570. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8sc01209a

Kekul diradicaloids derived from a classical N-heterocyclic carbeneElectronic supplementary... 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-iPr2C6H3)}2CH2CH2), 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 Kekul 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 singlettriplet energy gap EST for 5 (10.7 kcal mol1), while EST for 4 (29.1 kcal mol1) is rather large. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Chemical Science Royal Society of Chemistry

Kekul diradicaloids derived from a classical N-heterocyclic carbeneElectronic supplementary information (ESI) available. CCDC 18265671826570. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8sc01209a

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Publisher
Royal Society of Chemistry
Copyright
This journal is © The Royal Society of Chemistry
ISSN
2041-6520
D.O.I.
10.1039/c8sc01209a
Publisher site
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Abstract

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-iPr2C6H3)}2CH2CH2), 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 Kekul 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 singlettriplet energy gap EST for 5 (10.7 kcal mol1), while EST for 4 (29.1 kcal mol1) is rather large.

Journal

Chemical ScienceRoyal Society of Chemistry

Published: May 4, 2018

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