Transition-Metal Complexes with Nano-Sized Phosphine and Pyridine Ligands-Catalysis, Fluxional Behavior and Molecular Recognition

被引:0
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作者
Yasushi Obora
Makoto Tokunaga
Yasushi Tsuji
机构
[1] Hokkaido University,Catalysis Research Center and Division of Chemistry, Graduate School of Science
[2] CREST,undefined
[3] Japan Science and Technology Corporation (JST),undefined
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关键词
nano-sized ligand; dendrimer; calixarene; phosphine; pyridine; homogeneous catalysis; oxidation; hydrosilylation; ligand effect; molecular recognition;
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摘要
Nano-sized phosphine and pyridine ligands having tetraphenylphenyl-, m-terphenyl-, poly(benzylether) moieties were synthesized. These ligands showed a remarkable effect on homogeneous transition metal catalyzed reactions. Pd(II) complexes with tetraphenylphenyl substituted pyridine ligands show high catalytic activities for oxidation of ketones suppressing Pd black formation and maintains the catalytic activity for a long time. Rh(I) complex catalysts with m-terphenyl substituted phosphine ligands showed remarkable rate acceleration in the hydrosilylation of ketones. In addition, several phosphinocalixarene ligands were synthesized and their coordination studies with Pd(II), Pt(II), Ru(II), Ir(I), and Rh(I) metals were documented. Ir(I) and Rh(I) cationic complexes with a 1,3,5-triphosphinocalix[6]arene ligand showed dynamic behavior with size-selective molecular recognition.
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页码:259 / 268
页数:9
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