Preparation of a Compound with a SiII−SiIV−SiII Bonding Arrangement

• Published in: Chemistry : a European journal 2024-03, Vol.30 (14), p.e202303113-n/a
• Main Authors: Kushvaha, Saroj Kumar, Kallenbach, Paula, Gorantla, Sai Manoj N. V. T., Herbst‐Irmer, Regine, Stalke, Dietmar, Roesky, Herbert W.
• Format: Article
• Language: English
• Subjects: Chemical bonds; EDA-NOCV analysis; reactivity; silicon chemistry; silicon–silicon bonds; silylenes
• ISSN: 0947-6539; 1521-3765; 1521-3765
• DOI: 10.1002/chem.202303113

Herein, we report the synthesis of a rare bis‐silylene, 1, in which two SiIIatoms are bridged by a SiIV atom. Compound 1 contains an unusual SiII−SiIV−SiII bonding arrangement with SiII−SiIV bond distances of 2.4212(8) and 2.4157(7) Å. Treatment of 1 with Fe(CO)5 afforded a dinuclear Fe0 complex 2 with two unusually long Si−Si bonds (2.4515(8) and 2.4488(10) Å). We have also carried out a detailed computational study to understand the nature of the Si−Si bonds in these compounds. Natural bond orbital (NBO) and energy decomposition analysis–natural orbital for chemical valence (EDA‐NOCV) analyses reveal that the Si−Si bonds in 1 and 2 are of an electron‐sharing nature. Sharing bonds: This article reports a rare bis‐silylene, [LSi)2−SiPh2, L=(PhC(NtBu)2] (1), in which a SiIV atom bridges two silylene atoms. Compound 1 contains an unusual SiII−SiIV−SiII bonding arrangement with SiII−SiIV bond lengths of 2.4212(8) and 2.4157(7) Å. Treatment of 1 with Fe(CO)5 afforded a dinuclear Fe0 complex 2 with two unusually long Si−Si bonds (2.4515(8) and 2.4488(10) Å). NBO and EDA‐NOCV analyses reveal that the Si−Si bonds in 1 and 2 are of an electron‐sharing nature.