Catalytic Synthesis of Poly(arylmethylgermanes) by Demethanative Coupling: A Mild Route to σ-Conjugated Polymers
Catalytic Synthesis of Poly(arylmethylgermanes) by Demethanative Coupling: A Mild Route to σ-Conjugated Polymers
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通过脱甲烷偶联催化合成聚（芳基甲基锗烷）：一条温和的 σ-共轭聚合物路线
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发表时间：
1998
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通讯作者：
D. H. Berry
中科院分区：
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作者：
S. M. Katz;J. Reichl;D. H. Berry
以四（三甲基膦）二甲基钌为催化剂前体，通过温和催化脱甲烷偶联反应，以高收率合成了多种聚芳甲基锗烷。锗烷Me2GeArH（Ar =苯基、对甲苯基、对氟代、对三氟甲苯基、对茴香基和间二甲苯基）在室温下在纯单体中进行聚合。催化剂的去除可以通过用空气处理反应混合物来实现，这使得聚合物产率在70%和100%之间。或者，通过用甲醇从THF溶液中沉淀聚合物来分离催化剂得到较低的产率，但得到分子量稍高的材料。新的聚锗烷，其特征在于通过1H NMR和凝胶渗透色谱法（GPC）使用聚苯乙烯标准和光散射方法。通过聚苯乙烯分析计算的分子量落在Mw = 3 × 103至7 × 103和Mn = 2 × 103至6 × 103的范围内。由光散射得到的值是适用的。
A variety of poly(arylmethylgermanes) have been synthesized from aryldimethylgermanes in high yield via mild catalytic demethanative coupling using tetrakis(trimethylphosphine)dimethylruthenium as a convenient catalyst precursor. Polymerizations of germanes Me2GeArH (Ar = phenyl, p-tolyl, p-fluoro, p-trifluorotolyl, p-anisyl, and m-xylyl) proceed in neat monomer at room temperature. Catalyst removal can be effected by treatment of the reaction mixture with air, which gives polymer yields between 70% and 100%. Alternatively, separation of the catalyst by precipitation of the polymers from THF solution with methanol gives lower yields, but of somewhat higher molecular weight material. The new polygermanes are characterized by 1H NMR and by gel permeation chromatography (GPC) using both polystyrene standards and light scattering methods. Molecular weights calculated by polystyrene analysis fall in the ranges of Mw = 3 × 103 to 7 × 103 and Mn = 2 × 103 to 6 × 103. Values obtained from light scattering are app...