Substituent Effects on Ring Opening Allene Metathesis: Polymerization Rate Enhancement and Regioregularity

被引:4
作者
Neary, William J. [1 ]
Zhao, Fengyue [2 ]
Murphy, Megan C. [1 ]
Chen, Yu [3 ,4 ]
Liu, Fang [2 ]
Houk, K. N. [5 ]
Moore, Jeffrey S. [6 ,7 ]
机构
[1] Univ Illinois, Dept Chem, Urbana, IL 61801 USA
[2] Nanjing Agr Univ, Coll Sci, Nanjing 210095, Peoples R China
[3] Southern Univ Sci & Technol, Dept Chem, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Peoples R China
[4] Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Peoples R China
[5] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA
[6] Univ Illinois, Dept Chem, Urbana, IL 61801 USA
[7] Univ Illinois, Beckman Inst Adv Sci & Technol, Urbana, IL 61801 USA
基金
美国国家科学基金会;
关键词
AB-INITIO PSEUDOPOTENTIALS; THERMOCHEMISTRY; CHEMISTRY; ROMP;
D O I
10.1021/acs.macromol.4c00699
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Polyallenamers represent an emerging class of polymeric materials with highly tailorable and adaptive properties. While their generation has been achieved (via cross-coupling, postpolymerization modifications, and ring opening allene metathesis polymerization (ROAlMP)), molecular weight limitations and the inability to obtain precise microstructures have prevented the ability to utilize allenes to their full potential. Herein, we demonstrate the effects that allylic derivatization of cyclic allenes (4-R-1,2-CNDs) have on the polymerization rate and regioselectivity of ROAlMP. Bulky substituents were shown to favor the formation of distal products, leading to perfectly regioregular polymerizations (>97% head-to-tail). Kinetic investigations indicated that bulky substituents also led to large polymerization rate enhancements (>20x), allowing for the generation of high molecular weight material (M-n > 120 kDa) and effective chain extension. Density functional theory calculations indicate that bulky substituents destabilize the metallacyclobutane intermediate to a greater extent than the transition state (cycloreversion), leading to unprecedented rate enhancements.
引用
收藏
页码:5350 / 5357
页数:8
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