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Probing β-alkyl elimination and selectivity in polyolefin hydrogenolysis through DFT
Catalysis Science & Technology ( IF 4.4 ) Pub Date : 2021-08-16 , DOI: 10.1039/d1cy01088c Alexander Q. Kane 1 , Alec M. Esper 1 , Keith Searles 1 , Christian Ehm 2 , Adam S. Veige 1
Catalysis Science & Technology ( IF 4.4 ) Pub Date : 2021-08-16 , DOI: 10.1039/d1cy01088c Alexander Q. Kane 1 , Alec M. Esper 1 , Keith Searles 1 , Christian Ehm 2 , Adam S. Veige 1
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Polyolefin waste is constantly growing, and the few existing solutions for recycling, reuse, and degradation are not viable long term. Carbon–carbon bond scission is a highly sought-after technology to assist in reclaiming polymers. This work compiles and advances the understanding of β-alkyl elimination, a method of C–C cleavage, through DFT characterization on a model substrate, (S)-2,8-dimethyldecane, and silica-supported Zr–H catalyst, [(![[triple bond, length as m-dash]](https://www.rsc.org/images/entities/char_e002.gif)
SiO)3ZrH]. The primary goal is to examine selectivity in C–C bond cleavage events. σ-Bond metathesis favors C–H activation at methyl branches by ∼2 kcal mol−1. Chain walking via β-H elimination and insertion occurs readily and prefers E-alkene eliminations. β-Alkyl elimination also favors formation of E-alkene elimination products (∼2 kcal mol−1), β-Me elimination (∼1 kcal mol−1), and primary Zr–C cleavage (∼2 kcal mol−1) over Z-alkenes, β-R (R > CH3) elimination, and secondary Zr–C cleavage, respectively. These selectivity rules will help guide future experimental work and catalyst design.
中文翻译：
通过 DFT 探讨聚烯烃氢解中的 β-烷基消除和选择性
聚烯烃废物不断增加，现有的为数不多的回收、再利用和降解解决方案是不可行的。碳-碳键断裂是一种非常受欢迎的技术，可帮助回收聚合物。这项工作通过在模型底物（S）-2,8-二甲基癸烷和二氧化硅负载的 Zr-H 催化剂上进行 DFT 表征，汇编并促进了对 β-烷基消除（一种 C-C 裂解方法）的理解。SiO) 3 ZrH]。主要目标是检查 C-C 键裂解事件的选择性。σ-Bond 复分解有利于甲基支链处的 C-H 活化~2 kcal mol -1。通过β-H消除和插入的链行走很容易发生并且更喜欢E-烯烃消除。β-烷基消除也有利于形成E-烯烃消除产物（~2 kcal mol -1）、β-Me 消除（~1 kcal mol -1）和初级 Zr-C 裂解（~2 kcal mol -1）超过Z-烯烃、β-R (R > CH 3 ) 消除和二次 Zr-C 裂解分别。这些选择性规则将有助于指导未来的实验工作和催化剂设计。
更新日期：2021-08-19
SiO)3ZrH]. The primary goal is to examine selectivity in C–C bond cleavage events. σ-Bond metathesis favors C–H activation at methyl branches by ∼2 kcal mol−1. Chain walking via β-H elimination and insertion occurs readily and prefers E-alkene eliminations. β-Alkyl elimination also favors formation of E-alkene elimination products (∼2 kcal mol−1), β-Me elimination (∼1 kcal mol−1), and primary Zr–C cleavage (∼2 kcal mol−1) over Z-alkenes, β-R (R > CH3) elimination, and secondary Zr–C cleavage, respectively. These selectivity rules will help guide future experimental work and catalyst design.
中文翻译：
通过 DFT 探讨聚烯烃氢解中的 β-烷基消除和选择性
聚烯烃废物不断增加，现有的为数不多的回收、再利用和降解解决方案是不可行的。碳-碳键断裂是一种非常受欢迎的技术，可帮助回收聚合物。这项工作通过在模型底物（S）-2,8-二甲基癸烷和二氧化硅负载的 Zr-H 催化剂上进行 DFT 表征，汇编并促进了对 β-烷基消除（一种 C-C 裂解方法）的理解。
SiO) 3 ZrH]。主要目标是检查 C-C 键裂解事件的选择性。σ-Bond 复分解有利于甲基支链处的 C-H 活化~2 kcal mol -1。通过β-H消除和插入的链行走很容易发生并且更喜欢E-烯烃消除。β-烷基消除也有利于形成E-烯烃消除产物（~2 kcal mol -1）、β-Me 消除（~1 kcal mol -1）和初级 Zr-C 裂解（~2 kcal mol -1）超过Z-烯烃、β-R (R > CH 3 ) 消除和二次 Zr-C 裂解分别。这些选择性规则将有助于指导未来的实验工作和催化剂设计。
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