Long-Range Kinetic Effects on the Alternating Ring Opening Metathesis of Bicyclo[4.2.0]oct-6-ene-7-carboxamides and Cyclohexene

IF 3.3 Q2 CHEMISTRY, MULTIDISCIPLINARY
Francis O. Boadi,  and , Nicole S. Sampson*, 
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Abstract

We report an investigation of rates of ruthenium-catalyzed alternating ring opening metathesis (AROM) of cyclohexene with two different Ru-cyclohexylidene carbenes derived from bicyclo[4.2.0]oct-6-ene-7-carboxamides (A monomer) that bear different side chains. These monomers are propylbicyclo[4.2.0]oct-6-ene-7-carboxamide and N-(2-(2-ethoxyethoxy)ethanylbicyclo[4.2.0]oct-6-ene-7-carboxamide. The amide substitution of these monomers directly affects both the rate of the bicyclo[4.2.0]oct-6-ene-7-carboxamide ring opening and the rate of reaction of the resulting carbene with cyclohexene (B monomer). The resulting Ru-cyclohexylidenes underwent reversible ring opening metathesis with cyclohexene. However, the thermodynamic equilibrium disfavored cyclohexene ring opening. Utilization of triphenylphosphine forms a more stable PPh3 ligated complex, which suppresses the reverse ring closing reaction and allowed direct measurements of the forward rate constants for formation of various A-B and A-B-A′ complexes through carbene-catalyzed ring-opening metathesis and thus gradient polymer structure-determining steps. The relative rate of the propylbicyclo[4.2.0]oct-6-ene-7-carboxamide ring opening is 3-fold faster than that of the N-(2-(2-ethoxyethoxy)ethanylbicyclo[4.2.0]oct-6-ene-7-carboxamide. In addition, the rate of cyclohexene ring-opening catalyzed by the propyl bicyclooctene is 1.4 times faster than when catalyzed by the ethoxyethoxy bicyclooctene. Also, the subsequent rates of bicyclo[4.2.0]oct-6-ene-7-carboxamide ring opening by propyl-based Ru-hexylidene are 1.6-fold faster than ethoxyethoxy-based Ru-hexylidene. Incorporation of the rate constants into reactivity ratios of bicyclo[4.2.0]amide-cyclohexene provides prediction of copolymerization kinetics and gradient copolymer structures.

Abstract Image

双环[4.2.0]辛-6-烯-7-羧胺和环己烯交替开环复分解的远程动力学效应
我们报道了钌催化的环己烯与两种不同的Ru亚环己烯卡宾的交替开环复分解(AROM)速率的研究,这两种卡宾衍生自具有不同侧链的双环[4.2.0]辛-6-烯-7-甲酰胺(A单体)。这些单体是丙基双环[4.2.0]辛-6-烯-7-甲酰胺和N-(2-(2-乙氧基乙氧基)乙基双环[4.2.0]辛-6-烯-7甲酰胺。这些单体的酰胺取代直接影响双环[4.2.0%辛-6-烯7--甲酰胺的开环速率和所得卡宾与环己烯(B单体)的反应速率。得到的Ru亚环己基与环己烯进行可逆的开环复分解。然而,热力学平衡不利于环己烯开环。利用三苯基膦形成更稳定的PPh3连接的络合物,其抑制反向闭环反应,并允许通过卡宾催化的开环复分解和梯度聚合物结构确定步骤直接测量形成各种a-B和a-B-a′络合物的正向速率常数。丙基双环[4.2.0]辛-6-烯-7-甲酰胺的相对开环速率比N-(2-(2-乙氧基乙氧基)乙基双环[4.2.0]辛-6-烯-7甲酰胺快3倍。此外,丙基双环辛烯催化的环己烯开环速率是乙氧基甲氧基双环辛烯催化剂的1.4倍。此外,基于丙基的Ru亚己基随后的双环[4.2.0]辛-6-烯-7-甲酰胺开环速率是基于乙氧基乙氧基的Ru亚己基的1.6倍快。将速率常数并入双环[4.2.0]酰胺-环己烯的反应性比率中提供了共聚动力学和梯度共聚物结构的预测。
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来源期刊
ACS Organic & Inorganic Au
ACS Organic & Inorganic Au 有机化学、无机化学-
CiteScore
4.10
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0.00%
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0
期刊介绍: ACS Organic & Inorganic Au is an open access journal that publishes original experimental and theoretical/computational studies on organic organometallic inorganic crystal growth and engineering and organic process chemistry. Short letters comprehensive articles reviews and perspectives are welcome on topics that include:Organic chemistry Organometallic chemistry Inorganic Chemistry and Organic Process Chemistry.
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