“…Therefore, the two hfcc of 4.07 and 3.74 mT can be assigned to coupling with the 29 Si1 and 29 Si3 nuclei, and the hfcc of 1.55 mT is assigned to coupling with the 29 Si2 nucleus. The relatively low hfcc due to Si1 and Si3 atoms are consistent with the delocalization of the unpaired electron in the allylic system. , 2 ESR Spectrum of 1 • in heptane at 298 K.…”
“…Therefore, the two hfcc of 4.07 and 3.74 mT can be assigned to coupling with the 29 Si1 and 29 Si3 nuclei, and the hfcc of 1.55 mT is assigned to coupling with the 29 Si2 nucleus. The relatively low hfcc due to Si1 and Si3 atoms are consistent with the delocalization of the unpaired electron in the allylic system. , 2 ESR Spectrum of 1 • in heptane at 298 K.…”
“…Thus, we synthesized the known monochlorosilane 5b by addition of t -BuLi to dichlorophenylsilane. The freshly prepared and distilled monochlorosilane was then used to silylate lithiated bromopolystyrene to afford the shelf-stable silyl hydride resin 6b .…”
[reaction: see text] A new, robust tert-butyldiarylsilyl (TBDAS) linker has been developed for solid-phase organic synthesis. This linker is stable to both protic and Lewis acidic reaction conditions, overcoming a significant limitation of previously reported silyl linkers. Solid-phase acetal deprotection, olefination, asymmetric allylation, and silyl protecting group deblocking reactions have been demonstrated with TBDAS-linked substrates.
“…On the other hand, cyclopropene is one of the smallest ring compounds and has a highly strained energy − For more than a decade, we have investigated the chemistry of silicon-substituted cyclopropenes, such as hexasilylbicyclopropenyls and 4-silatriafulvenes . In the course of our study, we found the unexpected reactivity of a trihalosilyl-substituted cyclopropene.…”
Reduction of tri-tert-butyl-3-(tribromosilyl)cyclopropene with potassium graphite yielded
a unique lattice-framework disilene, a racemate of (4R,6R,4‘R,6‘R)- and (4S,6S,4‘S,6‘S)-2,3,4,6,7,8,2‘,3‘,4‘,6‘,7‘,8‘-dodeca-tert-butyl-[5,5‘]bi{1,5-disilatricyclo[4.2.0.01,4]octylidene}-2,7,2‘,7‘-tetraene (dl-2). Oxidation of dl-2 gave the corresponding 1,3,2,4-dioxadisiletane
derivative stereospecifically. Trapping experiments revealed that a thermal equilibrium
between dl-2 and the corresponding silylene, 2,3,4,6,7,8-hexa-tert-butyl-1,5-disilatricyclo[4.2.0.01,4]octa-2,7-diene-5,5-diyl (6), existed in solution at room temperature. Thus, the
intermediate 6 reacted with methanol, halides, and acetylenes to give the corresponding
methoxysilane, dihalosilanes, and silacyclopropenes, respectively. The reactions were
accelerated by irradiation. DFT calculations of dl-2 and the related compounds well
reproduced the experimental results of the thermal equilibrium between dl-2 and 6. TD-DFT calculations of dl-2 revealed that an intramolecular through-space interaction exists
between the π*Si
Si and π*C
C orbitals in the LUMO of dl-2, contributing to the stabilization
of the LUMO.
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