The generation of 1,1-dimethylsilanimine by flash vacuum thermolysis

Gas-Phase Characterization of Unhindered Silanimines by Photoelectron Spectroscopy: Experimental and Theoretical Study of the SiN Double Bond1

“…Reported methods have been used for the synthesis of precursors 2b , 2c and 2d , and 3d 6 . 1-Isopropyl-2,2,3-trimethyl-1-aza-2-silacyclobutane ( 3c ) has been prepared, in the way described for 3d , from N -allyl- N -isopropyl-1,1-dimethylsilanamine and purified by GC at 120 °C on a SE30 column [ 1 H NMR (CDCl 3 ): δ = 0.20 (s, 3 H), 0.25 (s, 3 H), 0.96 (d, J = 6.3 Hz, 6 H), 1.10 ((d, J = 7.6 Hz, 3 H), 1.53 (ddq, J = 8.4, 7.6 and 5.2 Hz, 1 H), 2.80 (dd, J = 6.3 and 5.2 Hz, 1 H), 2.83 (hept, J = 6.3 Hz, 1 H), 3.55 ppm (dd, J = 8.4 and 6.3 Hz, 1 H). 13 C NMR: δ = −0.84, 2.84, 15.00, 17.57, 22.99, 48.52, 55.84 ppm].…”

“…The comparative study of the thermolysis of two azasilacyclobutanes 3c , d is also presented: These precursors are expected to undergo a retro [2+2] cleavage into propene and silanimines.…”

Flash Vacuum Thermolysis: First Gas-Phase Generation of Unhindered Silylidenephosphanes and Characterization by Photoelectron Spectroscopy

“…In the last two decades, the use of flash vacuum thermolysis (FVT) has allowed the observation of many reactive, monomeric species having a double-bonded silicon atom, and we have reported the generation by FVT of several unstabilized silanimines , as well as, very recently, their unambiguous characterization by photoelectron spectroscopy (PES) . Our investigations have pointed out the usefulness of cyclodisilazanes and azasilacyclobutanes as precursors of these silanimines.…”

Flash Vacuum Thermolysis Synthesis of New Reactive Compounds Containing a Silicon−Heteroatom Double Bond

“…The intermediacy of 9 was confirmed by the obtaining of the expected adduct 15 with tert-butyl alcohol. [23,24] Silanimine 9, as well as di-and triphenylsilanimines, have been recently generated in matrix by photolysis of the corresponding silyl azides and characterized by IR and UV spectroscopy. [25] FVT of silanamine 16, a possible precursor of the unsubstituted silanimine 17 by retro-ene reaction and double β-elimination of isobutene, has also been investigated in conjunction with MWS.…”

“…Its intermediacy was also confirmed, in the presence of tertbutyl alcohol, by the formation of compound 15. [23,30] N-Alkylcyclo-1,3-disila-2,4-diazanes 25, 20 and 24 are known, stable and easily prepared compounds. [31] Upon FVT in conjunction with PES, 25 and 20 proved to be excellent precursors for the corresponding silanimines, undergoing as their only reactions equilibria with monomeric species 26 and 5, respectively (Scheme 5).…”