POLYMERIZATION OF ACETYLENES BY NICKEL-CARBONYL-PHOSPHINE COMPLEXES ..4. KINETICS AND POLYMERIZATION MECHANISMS
POLYMERIZATION OF ACETYLENES BY NICKEL-CARBONYL-PHOSPHINE COMPLEXES ..4. KINETICS AND POLYMERIZATION MECHANISMS
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DOI：
10.1021/jo01058a043
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发表时间：
1962-01-01
影响因子：
3.6
通讯作者：
KENNERLY, GW
中科院分区：
文献类型：
--
作者：
MERIWETHER, LS;COLTHUP, EC;KENNERLY, GW
报道了溶剂、温度、气体扫掠、乙炔-催化剂比和催化剂结构等因素对反应的影响。对Ni (CO) 2 (Ph3P) 2聚合1-庚炔和苯乙炔的动力学进行了研究，包括氘取代和催化剂预处理的影响。考虑了“活性”镍催化剂的可能结构。提出了单取代乙炔线性聚合和环聚的机理，与观察到的动力学、氘同位素效应和产物结构一致。本文还提出了二取代乙炔芳烃化反应的机理。在以前的文章中，我们讨论了不同种类的乙炔在镍-羰基-膦催化剂上的聚合反应，以及得到的芳香低聚物和线性低聚物的结构。考察了溶剂、温度、气体扫量、乙炔-催化剂比和催化剂结构等因素对聚合过程的影响。本文还介绍了这些反应的动力学研究结果，包括催化剂的预处理和氘同位素效应，以及对反应机理的结论。
The effects of variations in solvent, temperature and gas sweeping, acetylene-catalyst ratio, and catalyst structure are reported. A kinetic study has been made of the polymerization of 1-heptyne and phenylacetylene by Ni (CO) 2 (Ph3P) 2, including effects ofdeuterium substitution and catalyst pretreatment. Possible structures for the “active” nickel catalyst are considered. Mechanisms are proposed for the linear and cyclicpolymerization of monosubstituted acetylenes, which are consistent with the observed kinetic and deuterium isotope effects and product structures. A mechanism for the aro-matization of disubstituted acetylenes is also suggested.In previous papers2 we have discussed the polymerization of various classes of acetylenes with nickel-carbonyl-phosphine catalysts and the structures of the aromatic and linear oligomers obtained. The effects on the course of the polymerization due to changes in solvent, temperatureand gas sweeping, acetylene-catalyst ratio, and catalyst structure have now been examined. In this paper we also presentthe results of kinetic studies of these reactions, including pretreatment of catalyst and deuterium isotope effects, and conclusions regarding the reaction mechanisms.