Tetrahedral Sn–silsesquioxane: synthesis, characterization and catalysis

Abstract

A tetrahedral stannasilsesquioxane complex was synthesized as a racemic mixture using Sn(O(i)Pr)4 and silsesquioxanediol, and its structure was confirmed with X-ray crystallography, NMR, and EXAFS. The complex was a Lewis acid, and both anti and syn-binding with Lewis bases were possible with the formation of octahedral Sn complexes. It was also a Lewis acid catalyst active for epoxide ring opening and hydride transfer.

Heptanuclear Cage CuII‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity

“…Specific representatives of cage metallacomplexes, namely cagelike metallasilsesquioxanes (CLMSs), are being intensely studied as (pre)catalysts for numerous chemical processes of high relevance . Cage metallasilsesquioxanes were found to be active in alkene polymerization, epoxidation or epoxide ring opening, metathesis, hydroformylation, Ullmann–Goldberg condensation and amidation . Recently, significant attention was drawn to the potential of CLMS application in the homogeneous oxidation of C–H compounds with activity confirmed for Fe‐,, Cr‐, Ni‐, and Co‐based compounds.…”

Novel Cage-Like Hexanuclear Nickel(II) Silsesquioxane. Synthesis, Structure, and Catalytic Activity in Oxidations with Peroxides

“…Cage-like metallasilsesquioxanes (CLMSs) [1,2,3,4,5,6,7,8,9,10,11,12,13], being a family of polyhedra with inorganic (metal silicate-like) cores and organic environments, have been thoroughly investigated in the line of their potential application in catalysis [14,15,16,17]. Nevertheless, their capacities as catalysts of oxidation processes remain in the shadow until recent past.…”

New materials for catalysis and energy storage devices

“…Figure shows one such T d Sn complex I , in which the T d coordination was stabilized by sandwiching the Sn ion between two bulky, siliceous units derived from incompletely condensed polyhedral oligomeric silsesquioxane (POSS, R 7 Si 7 O 9 (OH) 3 , where R is a cyclohexyl or an isobutyl group). The structure of this soluble complex could be determined with certainty with a combination of X‐ray crystallography and spectroscopy . The POSS ligands provided sufficient steric hindrance to maintain Sn in the T d coordination, yet formed a structure sufficiently open to allow coordination expansion of the Sn center in the presence of strongly interacting small molecules.…”