Introduction of organogermyl functionalities to cage silsesquioxanes
In this work, we present the first example of highly efficient platinum-catalyzed hydrosilylation of vinyl- and allylgermanes with different types of silsesquioxanes and spherosilicates. This protocol allows the straightforward introduction of organogermyl functionalities with alkyl chains linked to the silsesquioxane core with good yields and excellent selectivity. These derivatives may be applied as precursors for the development of advanced hybrid materials in the future. In addition, a comparison made between vinylsilanes and vinylgermanes showed a higher reactivity of germanium compounds in the hydrosilylation reaction. To the best of our knowledge, this is the first literature example of the functionalization of silsesquioxanes and spherosilicates with these types of germanium derivatives. The reaction parameters and kinetics were determined by in situ FT-IR. In addition, our research is supported by extensive data obtained from NMR measurements.
Palladium complex-catalyzed germylation of allylic halides using (germyl)stannanes
(Triethylgermyl)tributylstannane reacts metal-selectively with allylic halides at room temperature (r.t.) in the presence of tris(dibenzylideneacetone)dipalladium, Pd2(dba)3CHCl3, to provide an alternative route to allylge
Palladium-catalyzed dehalogenative germylation of allylic halides with triethylgermyltributylstannane at room temperature
Triethylgermyltributylstannane was found to react with allylic halides at room temperature in the presence of a catalytic amount of Pd2(dba)3CHCl3 to bring about regioselective dehalogenative germylation giving 2-alkenyltriethylgermanes in good yields. Using triphenylphosphine as a ligand of the palladium caused to slow the rate of the present reaction.
Nakano, Taichi,Ono, Kazuyoshi,Migita, Toshihiko
p. 697 - 698
(2007/10/03)
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