用于苯乙炔立体选择性聚合的自支撑有机金属铑醌纳米催化剂。

Self-supported organometallic rhodium quinonoid nanocatalysts for stereoselective polymerization of phenylacetylene.

作者信息

Park Kang Hyun, Jang Kwonho, Son Seung Uk, Sweigart Dwight A

机构信息

Department of Chemistry, Sungkyunkwan University, Suwon 440-746, Korea.

出版信息

J Am Chem Soc. 2006 Jul 12;128(27):8740-1. doi: 10.1021/ja062907o.

DOI:10.1021/ja062907o

PMID:16819862

Abstract

Heterogeneous self-supported organometallic nanocatalysts (ONs) were synthesized by treatment of the eta6-pi-hydroquinone rhodium complex [(1,4-hydroquinone)Rh(COD)]+ with Al(Oi-Pr)3. The organometallic nanocatalysts, the size of which can be controlled by alteration of the reaction conditions, show high catalytic activities in the stereoselective polymerization of phenylacetylene to produce cis-poly(phenylacetylene). A key feature of the ON catalyst synthesis is a facile eta6 to eta4 hapticity change occurring in the quinonoid ring, which is triggered by deprotonation of the -OH groups by Al(Oi-Pr)3, with concomitant coordination of the quinone oxygen atoms to the aluminum.

摘要

通过用异丙醇铝（Al(Oi-Pr)3）处理η6-π-对苯二酚铑配合物[(1,4-对苯二酚)Rh(COD)]+合成了多相自支撑有机金属纳米催化剂（ONs）。该有机金属纳米催化剂的尺寸可通过改变反应条件来控制，在苯乙炔的立体选择性聚合反应中表现出高催化活性，生成顺式聚（苯乙炔）。ON催化剂合成的一个关键特征是醌环中发生了从η6到η4配体配位变化，这是由Al(Oi-Pr)3使-OH基团去质子化引发的，同时醌氧原子与铝配位。