Ruthenium-Immobilized Periodic Mesoporous Organosilica: Synthesis, Characterization, and Catalytic Application for Selective Oxidation of Alkanes.
Periodic mesoporous organosilica (PMO) is a unique material that has a crystal-like wall structure with coordination sites for metal complexes. A Ru complex, [RuCl2 (CO)3 ]2 , is successfully immobilized onto 2,2'-bipyridine (BPy) units of PMO to form a single-site catalyst, which has been confirmed by various physicochemical analyses. Using NaClO as an oxidant, the Ru-immobilized PMO oxidizes the tertiary C-H bonds of adamantane to the corresponding alcohols at 57 times faster than the secondary C-H bonds, thereby exhibiting remarkably high regioselectivity. Moreover, the catalyst converts cis-decalin to cis-9-decalol in a 63 % yield with complete retention of the substrate stereochemistry. The Ru catalyst can be separated by simple filtration and reused without loss of the original activity and selectivity for the oxidation reactions.
Catalysis Research Center, Hokkaido University, Sapporo, Hokkaido 001-0021 (Japan).|Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo, Hokkaido 060-8628 (Japan).|Japan Science and Technology Agency (JST)/ACT-C, Nagakute, Aichi 480-1192 (Japan).
Nobuhiro
N
Ishito
Catalysis Research Center, Hokkaido University, Sapporo, Hokkaido 001-0021 (Japan).|Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo, Hokkaido 060-8628 (Japan).
Hirokazu
H
Kobayashi
Catalysis Research Center, Hokkaido University, Sapporo, Hokkaido 001-0021 (Japan).|Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo, Hokkaido 060-8628 (Japan).
Kiyotaka
K
Nakajima
Toyota Central R&D Laboratories Inc., Nagakute, Aichi 480-1192 (Japan).|Japan Science and Technology Agency (JST)/ACT-C, Nagakute, Aichi 480-1192 (Japan).
Yoshifumi
Y
Maegawa
Toyota Central R&D Laboratories Inc., Nagakute, Aichi 480-1192 (Japan).|Japan Science and Technology Agency (JST)/ACT-C, Nagakute, Aichi 480-1192 (Japan).
Shinji
S
Inagaki
Catalysis Research Center, Hokkaido University, Sapporo, Hokkaido 001-0021 (Japan).|Japan Science and Technology Agency (JST)/ACT-C, Nagakute, Aichi 480-1192 (Japan).|School of Engineering, Tokyo University of Technology, Hachioji, Tokyo 192-0982 (Japan).
Kenji
K
Hara
Catalysis Research Center, Hokkaido University, Sapporo, Hokkaido 001-0021 (Japan). fukuoka@cat.hokudai.ac.jp.|Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo, Hokkaido 060-8628 (Japan). fukuoka@cat.hokudai.ac.jp.
Atsushi
A
Fukuoka
adamantine; alkane; oxidation; periodic mesoporous organosilica; ruthenium