新型无钽配体催化剂体系用于乙烯的高选择性三聚反应生成 1-己烯：金属环机理的新证据。
New tantalum ligand-free catalyst system for highly selective trimerization of ethylene affording 1-hexene: new evidence of a metallacycle mechanism.
机构信息
Department of Chemistry, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan.
出版信息
J Am Chem Soc. 2009 Apr 22;131(15):5370-1. doi: 10.1021/ja8100837.
PMID:20560633
Abstract
Mild and salt-free reduction of MCl(5) (M = Nb, Ta) has been achieved by using 3,6-bis(trimethylsilyl)-1,4-hexadiene derivatives as reducing reagents. The salt-contact-free low-valent TaCl(3) exhibits high catalytic activity for the trimerization of ethylene to 1-hexene (>1000 TOF) with excellent selectivity (>98%). This salt-free tantalum system enables us to observe new evidence for a metallacycle mechanism.
摘要
通过使用 3,6-双(三甲基硅基)-1,4-己二烯衍生物作为还原剂，实现了 MCl(5) (M = Nb, Ta) 的温和无盐还原。这种无盐接触的低价 TaCl(3) 对乙烯三聚生成 1-己烯具有很高的催化活性(>1000TOF)，且选择性极好(>98%)。这种无盐的钽体系使我们能够观察到金属环机理的新证据。
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