Showing papers by "Chizuko Kabuto published in 2008"

Introduction of clutch function into a molecular gear system by silane-silicate interconversion.

Abstract: Introduction of the clutch-declutch mechanism into a new gear system, bis(4-methyl-9-triptycyl)difluorosilane 1, is achieved by the reversible attachment of fluoride ion giving the corresponding fluorosilicate 2. Although the phase isomers of 1 (1(dl) and 1(meso)) cannot be separated because of the equilibrium via a slow gear slippage process (DeltaH(double dagger) = 17.2 +/- 0.2 kcal x mol(-1) and DeltaS(double dagger) = 0.9 +/- 0.9 cal x mol(-1) x K(-1)), 1 works as meshed molecular gears in solution at room temperature. On the other hand, silicate 2 in the solid state has quite an unusual TBP structure having two organic triptycyl groups at the apical positions and three electronegative fluorine atoms at the equatorial positions against the Muetterties rule. Rotation of the two triptycyl groups around Si-C bonds in 2 is facile and independent to each other in solution. Silicate 2 is reverted to the corresponding silane mixture by treating with excess water.

Fourteen-electron bis(dialkylsilylene)palladium and twelve-electron bis(dialkylsilyl)palladium complexes.

Abstract: Stable transition-metal complexes with divalent silicon ligands (silylene complexes) have been extensively studied because of their important role in many catalytic processes. Since the pioneering works by Zybill et al. and Tilley et al. , various base-stabilized and base-free silylene complexes have been synthesized and their versatile reactivity has been well explored. Although complexes with two or more silylene ligands are expected to show interesting bonding properties and reactivities that are not observed in monosilylene complexes, such complexes are still limited to donorbridged bis(silylene) complexes and complexes having cyclic diaminosilylenes as ligands. During the course of our study on the application of dialkylsilylene 1, which is the

1,3-Digermabicyclo[1.1.0]butane with an Inverted Bridge Ge–Ge σ Bond

Abstract: 1,3-Digermabicyclo[1.1.0]butane 2 was synthesized as yellow crystals. The molecular structure, 13C NMR and UV–vis spectra, and theoretical calculations have revealed that 2 is a typical long bond i...