1665-01-6Relevant articles and documents
[Cl@Si20H20]-: Parent Siladodecahedrane with Endohedral Chloride Ion
Bamberg, Marcel,Bolte, Michael,Brandl, Matthias,Bursch, Markus,Grimme, Stefan,Hansen, Andreas,Kunze, Lukas,Lerner, Hans-Wolfram,Sentis, Gabriele,Wagner, Matthias
, p. 10865 - 10871 (2021)
Fullerenes and diamondoids are at the core of nanoscience. Comparable monodisperse silicon analogues are scarce. Herein, we report the synthesis of the parent siladodecahedrane, which represents the largest Platonic solid. It shares its pattern of pentagonal faces with the smallest fullerene, C20, and its saturated, H-terminated skeleton with diamondoids. Similar to endofullerenes, the silicon cage encapsulates a chloride ion ([Cl@Si20H20]-); similar to diamondoids, its Si-H termini offer a wealth of opportunities for further functionalization. Mere treatment with chloromethanes leads to the perchlorinated cluster [Cl@Si20Cl20]-. Both compounds were characterized by mass spectrometry, X-ray crystallography, NMR spectroscopy, and quantum-chemical calculations. The experimentally determined 35Cl resonances of the endohedral chloride ions are particularly diagnostic to probe the Cl- → Si20 interaction strength as a function of the different surface substituents, as we have proven by high-level computational analyses.
Involvement of Exciplexes in the Photolysis of Aliphatic Ketones in Deuteriochloroform: CIDNP Evidence
Zhang, Mao-Xi,Liu, Zhong-Li,Wu, Lung-Min,Liu, You-Cheng
, p. 451 - 454 (1989)
Photolysis of 4-acetyl-4-ethoxyformylcyclohexanone and 4-acetyl-4-phenylcyclohexanone in deuteriochloroform showed an unusual polarization which suggests that a singlet exciplex of the ketone with deuteriochloroform may be involved in the Norrish type I reaction.KEY WORDS - Photolysis Ketones CIDNP Exciplex
Kinetics of reactions of CN with chlorinated methanes
Samant, Vaishali,Hershberger, John F.
experimental part, p. 64 - 67 (2009/02/04)
The kinetics of reactions of CN with the chlorinated methanes CH3Cl, CH2Cl2, CHCl3 and CCl4 were investigated over the temperature range 298-573 K, using laser induced fluorescence (LIF) spectroscopy. At 298 K, rate constants of 9.0 ± 0.3 × 10-13, 8.8 ± 0.4 × 10-13, 9.0 ± 0.5 × 10-13 and 4.3 ± 0.6 × 10-13 cm3 molecule-1 s-1 were measured, respectively. A small positive temperature dependence was observed, as well as kinetic isotope effects of kH/kD ~ 2.14-2.25. These data along with product detection experiments strongly suggest that hydrogen abstraction dominates these reactions.