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Toyao, Takashi,Miyahara, Kenta,Fujiwaki, Mika,Kim, Tae-Ho,Dohshi, Satoru,Horiuchi, Yu,Matsuoka, Masaya American Chemical Society 2015 JOURNAL OF PHYSICAL CHEMISTRY C - Vol.119 No.15
<P>A catalytically competent Cu species has been immobilized within the framework of a Zr-based metal–organic framework with bipyridine units, Zr-MOF-bpy, by a simple postsynthetic modification method from CuBr<SUB>2</SUB> (Zr-MOF-bpy-CuBr<SUB>2</SUB>) and used for the selective oxidation of cyclooctene to cyclooctene oxide. Zr-MOF-bpy was synthesized by a simple solvothermal method and was shown to have a UiO-type structure. Diffuse reflectance UV–vis and XAFS measurements have revealed that the immobilized Cu species has a square-planar geometry of two N atoms and two Br atoms. Zr-MOF-bpy-CuBr<SUB>2</SUB> catalyzed the selective oxidation of cyclooctene to cyclooctene oxide with high activity and selectivity in the presence of <I>tert</I>-butyl hydroperoxide as an oxidant. In addition, the catalytic ability of Zr-MOF-bpy-CuBr<SUB>2</SUB> was demonstrated to be superior to that of the corresponding homogeneous catalyst ((bpy)CuBr<SUB>2</SUB>). It was also confirmed that Zr-MOF-bpy-CuBr<SUB>2</SUB> can be reused as a heterogeneous catalyst without significant loss of its activity and selectivity.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/jpccck/2015/jpccck.2015.119.issue-15/jp512749y/production/images/medium/jp-2014-12749y_0009.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/jp512749y'>ACS Electronic Supporting Info</A></P>