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Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
Published on: April 19, 2019
Isolation of an Annulated 1,4-Distibabenzene Diradicaloid
Henric Steffenfauseweh1, Dennis Rottschäfer1,2, Yury V Vishnevskiy1
1Molecular Inorganic Chemistry and Catalysis, Inorganic and Structural Chemistry, Center for Molecular Materials, Faculty of Chemistry, Universität Bielefeld, Universitätsstrasse 25, 33615, Bielefeld, Germany.
Abstract:
The first 1,4-distibabenzene-1,4-diide compound [(ADC)Sb]2 (5) based on an anionic dicarbene (ADC) (ADC=PhC{N(Dipp)C}2 , Dipp=2,6-iPr2 C6 H3 ) is reported as a bordeaux-red solid. Compound 5, featuring a central six-membered C4 Sb2 ring with formally SbI atoms may be regarded as a base-stabilized cyclic bis-stibinidene in which each of the Sb atoms bears two lone-pairs of electrons. 5 undergoes 2 e-oxidation with Ph3 C[B(C6 F5 )4 ] to afford [(ADC)Sb]2 [B(C6 F5 )4 ]2 (6) as a brick-red solid. Each of the Sb atoms of 6 has an unpaired electron and a lone-pair. The broken-symmetry open-shell singlet diradical solution for (6)2+ is calculated to be 2.13 kcal mol-1 more stable than the closed-shell singlet. The diradical character of (6)2+ according to SS-CASSCF (state-specific complete active space self-consistent field) and UHF (unrestricted Hartree-Fock) methods amounts to 36 % and 39 %, respectively. Treatments of 6 with (PhE)2 yield [(ADC)Sb(EPh)]2 [B(C6 F5 )4 ]2 (7-E) (E=S or Se). Reaction of 5 with (cod)Mo(CO)4 affords [(ADC)Sb]2 Mo(CO)4 (8).
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