Transition-Metal Complexes with Nano-Sized Phosphine and Pyridine Ligands-Catalysis,Fluxional Behavior and Molecular Recognition |
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| Authors: | Yasushi Obora Makoto Tokunaga Yasushi Tsuji |
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| Institution: | (1) Catalysis Research Center and Division of Chemistry, Graduate School of Science, Hokkaido University, CREST, Japan Science and Technology Corporation (JST), Sapporo 001-0021, Japan |
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| Abstract: | 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-triphosphinocalix6]arene ligand showed dynamic
behavior with size-selective molecular recognition. |
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| Keywords: | nano-sized ligand dendrimer calixarene phosphine pyridine homogeneous catalysis oxidation hydrosilylation ligand effect molecular recognition |
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