Synthesis of bimetallic cage-like metalloorganosiloxanes from polymeric metallosiloxanes

Cooperative Effect of Two Metals: CoPd(OAc)4‐Catalyzed CH Amination and Aziridination

“…All previously described approaches to the synthesis of cage‐like metallasilsesquioxanes use monomeric metal‐containing compounds as initial reagents 1,4. Recently, we have proposed a new convenient route to metallasilsesquioxanes 46. The idea of this method comprises partial cleavage of easily accessible polymeric metallasilsesquioxanes with subsequent assembly of the cage in the coordination sphere of the transition metal ion.…”

Binuclear Cage‐Like Copper(II) Silsesquioxane (“Cooling Tower”) – Its High Catalytic Activity in the Oxidation of Benzene and Alcohols

“…with a copper concentration that is three times higher) gave us copper metallasilsesquioxane of principally different "Globule-like" cage geometry described in ref. [46] Thus, we can conclude that peculiarities of the cage aggregation depend on the ratio of the reactants rather than on the features of the initial poly- mer architecture, the "magic ratio" 3:1 leading to the formation of the "Cooling Tower" structure.…”

“…[1,4] Recently, we have proposed a new convenient route to metallasilsesquioxanes. [46] The idea of this method comprises partial cleavage of easily accessible polymeric metallasilsesquioxanes with subsequent assembly of the cage in the coordination sphere of the transition metal ion. In this paper, we develop and modify this approach using newly synthesized sym-cis-tetraphenylcyclotetrasiloxanolate nonaethanolate [PhSi(O)-O -] 4 (Na + ) 4 (EtOH) 9 (1) as a nucleophile for polymeric copper silsesquioxane cleavage.…”

Modern concepts and methods in the chemistry of polyhedral metallasiloxanes

“…[81]. In contrast to the strategy described above (Scheme 17), the formation of polyhedral molecule proceeds due to the partial decomposition of the polycyclic oligomer.…”

“…However, the obvious limitation of this approach is the obligatory formation of PHMSs containing both polyvalent and alkali metals. The possibility of a new procedure was confirmed by the synthesis of PHMSs 38 and 39, which were originally obtained by traditional methods (Scheme 17) [81]. This process includes the progressive introduction of sodium organosilanolate, which splits siloxane fragments and integrates into the structure.…”