Tris(trimethylsilyl)methyl—a relatively stable saturated organic radical

An INDO study of the hyperfine coupling constants and equilibrium geometries of some tetra-atomic radicals

“…There is some experimental evidence that this is in fact the case. We have found a ~gsi coupling constant of 65 G [6] in Si(SiMe3) 3 compared with a 13C splitting of 26 G in C(SiMe3)3 [18]. Both these radicals are believed to be planar.…”

Formation of Trichlorosilyl‐Substituted Carbon‐Centered Stable Radicals through the Use of π‐Accepting Carbenes

“…[1] Already in 1970, Bassindale et al had reported the persistent tris(trimethylsilyl)methyl radical, [2] (Me 3 Si) 3 CC, which has a lifetime of several days at 298 K. The groups of Ingold, [3] Apeloig, [4] Bravo-Zhivotovskii, [5] Lee, [6] Sekiguchi, [7] and others [4][5][6] have shown that the lifetime of the radicals largely depends on the steric bulk of the substituents. In 2002, Sekiguchi et al [7] reported the first stable silicon-centered radical without any p conjugation.…”

Arenechromiumtricarbonyl complexes of silyl(germyl)(stannyl)- and silyl(germyl)(plumbyl)methanes including the unexpected formation of arenechromiumtricarbonyldimethylsilanol, (η6-C6H5)Cr(CO)3SiMe2OH

“…Indeed the NMR spectral analysis of the liquid obtained after removing the butyl ether did exhibit the expected 119 Sn resonance at 13.3 ppm assigned to Me 3 SnCH 2 GeMe 3 [7e]. Complex 7 was characterized by NMR spectroscopy and recrystallization from toluene afforded yellow crystals suitable for X-ray crystallography, vide infra .…”

“…Hexamethylphoshoramide (HMPA) was distilled over calcium oxide. t -Butyllithium (1.7 M in pentane), Me 3 SnCl and Cr(CO) 6 were purchased from Aldrich Chemicals; Me 3 SiCH 2 Cl and Me 3 GeCl were purchased from Gelest; Me 3 PbBr was obtained from the bromination of Me 4 Pb [21], PhMe 2 SiCH 2 GeMe 3 , 1 [7d], PhMe 2 Si(Me 3 Ge)(Me 3 Sn)CH, 2 [5] were synthesized by the reported methods. NMR spectra were recorded on Bruker 300 MHz spectrometer using CDCl 3 for 2 and 3 and using C 6 D 6 for 4–7 .…”

“…They are also versatile reagents in synthetic chemistry [3, 4] and for example, functionalized allylic silanes have been synthesized in high yield from the reaction of tris(trimethylsilyl)methyl borane (Me 3 Si) 3 CBH 2 with alkenyl lithium reagent [4]. However, related heteroleptic systems with differing group 14 groups have received only scant attention [5–7]. We and Shimizu group reported the synthesis of mixed group 14 methanes, (Me 3 Si)(Me 3 Ge) (Me 3 Sn)CH [5, 6].…”