Approach to the "Missing" Diarylsilylene: Formation, Characterization, and Intramolecular C–H Bond Activation of Blue Diarylsilylenes with Bulky Rind Groups †.

The treatment of the bulky Rind-based dibromosilanes, (Rind)₂SiBr₂ (2) [Rind = 1,1,7,7-tetra-R¹-3,3,5,5-tetra-R²-s-hydrindacen-4-yl: EMind (a: R¹ = Et, R² = Me) and Eind (b: R¹ = R² = Et)], with two equivalents of ^tBuLi in Et₂O at low temperatures resulted in the formation of blue solutions derived from the diarylsilylenes, (Rind)₂Si: (3). Upon warming the solutions above −20 °C, the blue color gradually faded, accompanying the decomposition of 3 and yielding cyclic hydrosilanes (4) via intramolecular C–H bond insertion at the Si(II) center. The molecular structures of the bulky Eind-based 3b and 4b were confirmed by X-ray crystallography. Thus, at −20 °C, blue crystals were formed (Crystal-A), which were identified as mixed crystals of 3b and 4b. Additionally, colorless crystals of 4b as a singular component were isolated (Crystal-B), whose structure was also determined by an X-ray diffraction analysis. Although the isolation of 3 was difficult due to their thermally labile nature, their structural characteristics and electronic properties were discussed based on the experimental findings complemented by computational results. We also examined the hydrolysis of 3b to afford the silanol, (Eind)₂SiH(OH) (5b). [ABSTRACT FROM AUTHOR]