Synthesis of Me BICAAC Supported Si(III) Radicals and a Silylone via Reduction Route From Me BICAAC-Si(IV) Precursors

• Published in: Chemistry, an Asian journal an Asian journal, 2024-11, Vol.19 (22), p.e202400730
• Main Authors: Kumar Thakur, Sandeep, De, Sriman, Adhikari, Manu, Manar, Krishna K, Koley, Debasis, Singh, Sanjay
• Format: Article
• Language: English
• ISSN: 1861-4728; 1861-471X
• DOI: 10.1002/asia.202400730

Past one decade has witnessed a tremendous growth in the field of carbene stabilized low-valent silicon compounds unravelling very exciting properties of these molecules. Herein, we have employed a bicyclic (alkyl)(amino)carbene, ( BICAAC) to explore the low-valent chemistry of silicon. The reduction of bicyclic (alkyl)(amino)carbene-SiCl complex, [( BICAAC)SiCl ] (1) with KC afforded low-valent Si complexes, including Si(III) radical [( BICAAC)SiCl ] (2) and a complex with silicon center in a formal zero-valent state, [( BICAAC) Si] (3). Similarly, the reduction of in-situ generated BICAAC adduct of Me SiCl with one equivalent of KC led to the formation of [( BICAAC)SiMe Cl] (4) complex having an unpaired electron. These complexes have been characterized by IR, UV-Vis., NMR, HRMS, EPR and their solid-state structures were also elucidated by single crystal X-ray crystallography. Further, DFT calculations revealed the lower energy singlet state for complexes 1, 3 and doublet state for complexes 2, 4.