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Heptanuclear Cage Cu II ‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity
Author(s) -
Bilyachenko Alexey N.,
Levitsky Mikhail M.,
Korlyukov Alexander A.,
Khrustalev Victor N.,
Zubavichus Yan V.,
Shul'pina Lidia S.,
Shubina Elena S.,
Vologzhanina Anna V.,
Shul'pin Georgiy B.
Publication year - 2018
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201701340
Subject(s) - chemistry , catalysis , yield (engineering) , hydrogen peroxide , alkyl , medicinal chemistry , pyrazine , acetophenone , alcohol , peroxide , cage , polymer chemistry , inorganic chemistry , organic chemistry , materials science , mathematics , combinatorics , metallurgy
Two prismatic phenyl‐ (PhSiO 1.5 ) 14 (CuO) 7 ( 1 , 29 % yield) and methyl‐ (MeSiO 1.5 ) 14 (CuO) 7 ( 2 , 19 % yield) heptacoppersilsesquioxanes were obtained by the interaction of Cu,Na‐based cage silsesquioxanes [(RSiO 1.5 ) 12 (CuO) 4 (NaO 0.5 ) 4 ] (R = Ph, Me) with 4,4′‐bipyridine and pyrazine, respectively, acting as “silent witness” ligands. Unusual molecular topologies of both compounds 1 and 2 , which are the first representatives of cage silsesquioxanes with seven metal ions in their cores, were established by X‐ray diffraction studies. Complex 1 was found to be an active precatalyst in the oxidation of alkanes and 1‐phenylethanol to alkyl hydroperoxides and acetophenone, respectively. Alkanes were oxidized by hydrogen peroxide, and the alcohol was oxidized by tert ‐butyl hydroperoxide.