Details

Autor(en) / Beteiligte

• Yildiz, Cem B.
• Leszczyńska, Kinga I.
• González‐Gallardo, Sandra
• Zimmer, Michael
• Azizoglu, Akin
• Biskup, Till
• Kay, Christopher W. M.
• Huch, Volker
• Rzepa, Henry S.
• Scheschkewitz, David

Titel

Equilibrium Formation of Stable All‐Silicon Versions of 1,3‐Cyclobutanediyl

Ist Teil von

• Angewandte Chemie International Edition, 2020-08, Vol.59 (35), p.15087-15092

Auflage

International ed. in English

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2020

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• Main group analogues of cyclobutane‐1,3‐diyls are fascinating due to their unique reactivity and electronic properties. So far only heteronuclear examples have been isolated. Here we report the isolation and characterization of all‐silicon 1,3‐cyclobutanediyls as stable closed‐shell singlet species from the reversible reactions of cyclotrisilene c‐Si3Tip4 (Tip=2,4,6‐triisopropylphenyl) with the N‐heterocyclic silylenes c‐[(CR2CH2)(NtBu)2]Si: (R=H or methyl) with saturated backbones. At elevated temperatures, tetrasilacyclobutenes are obtained from these equilibrium mixtures. The corresponding reaction with the unsaturated N‐heterocyclic silylene c‐(CH)2(NtBu)2Si: proceeds directly to the corresponding tetrasilacyclobutene without detection of the assumed 1,3‐cyclobutanediyl intermediate. Stable homonuclear tetrasila‐1,3‐cyclobutanediyls analogues are obtained from the equilibrium reactions of a cyclotrisilene and saturated N‐heterocyclic silylenes (c‐[(CR2CH2)(NtBu)2]Si: (R=H, Me)). Solid state structures show essentially planar four‐membered Si4 ring systems. Despite the long distance between the formal radical centers calculations suggest an unsupported π‐bond between them.