Catalytic and Stoichiometric Reactions by Half-metallocene Diene Complexes of Niobium and Tantalum

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概要

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• We have systematically prepared ethylene, benzyne, and alkylidene complexes of niobium and tantalum bearing the fragments of MCp (η<SUP>4</SUP>-1, 3-diene) (M = Nb and Ta), and we found that these complexes have the similar stereochemistry and reactivity to that observed for the corresponding metallocene complexes of Group 4 metals, indicating clearly that the fragments of half-metallocene diene were isoelectronic and isolobal to those of MCp<SUB>2</SUB> (M = Zr and Hf). According to these results, we found three kinds of polymerization of ethylene, norbornene, and methyl methacrylate by using half-metallocene complexes of niobium and tantalum. Mono (diene) complexes 2 and 14 and bis (diene) complexes 16 and 17 upon being activated by MAO catalyzed the living polymerization of ethylene. Di (benzyl) tantalum complexes 18 and 23 served as a unique stereoselective polymerization of norbornene. The half-metallocene tantalum complexes 42 bearing MMA and DAD ligands reacted with one equiv of AlMe<SUB>3</SUB> at -20°C to give a zwitter inonic hetero-bimetallic enolate species 43, which catalyzed the living polymerization of MMA.

• 社団法人 有機合成化学協会の論文
• 2004-11-01

著者

• MASHIMA Kazushi

  Department of Chemistry, Graduate School of Engineering Science, Osaka University

• Mashima Kazushi

  Department Of Chemistry Graduate School Of Engineering Science Osaka University

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