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Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
Published on: April 19, 2019
Isolation of an Arsenic Diradicaloid with a Cyclic C2 As2 -Core
Henric Steffenfauseweh1, Yury V Vishnevskiy1, Beate Neumann1
1Molecular Inorganic Chemistry and Catalysis, Inorganic and Structural Chemistry, Center for Molecular Materials, Faculty of Chemistry, Universität Bielefeld, Universitätsstr. 25, 33615, Bielefeld, Germany.
Abstract:
Herein, we report on the synthesis, characterization, and reactivity studies of the first cyclic C2 As2 -diradicaloid {(IPr)CAs}2 (6) (IPr = C{N(Dipp)CH}2 ; Dipp = 2,6-iPr2 C6 H3 ). Treatment of (IPr)CH2 (1) with AsCl3 affords the Lewis adduct {(IPr)CH2 }AsCl3 (2). Compound 2 undergoes stepwise dehydrochlorination to yield {(IPr)CH}AsCl2 (3) and {(IPr)CAsCl}2 (5 a) or [{(IPr)CAs}2 Cl]OTf (5 b). Reduction of 5 a (or 5 b) with magnesium turnings gives 6 as a red crystalline solid in 90% yield. Compound 6 featuring a planar C2 As2 ring is diamagnetic and exhibits well resolved NMR signals. DFT calculations reveal a singlet ground state for 6 with a small singlet-triplet energy gap of 8.7 kcal mol-1 . The diradical character of 6 amounts to 20% (CASSCF, complete active space self consistent field) and 28% (DFT). Treatments of 6 with (PhSe)2 and Fe2 (CO)9 give rise to {(IPr)CAs(SePh)}2 (7) and {(IPr)CAs}2 Fe(CO)4 (8), respectively.
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