南方科技大学知识苑(SUSTech KC): Substituent Effects on Ring Opening Allene Metathesis: Polymerization Rate Enhancement and Regioregularity

题名	Substituent Effects on Ring Opening Allene Metathesis: Polymerization Rate Enhancement and Regioregularity
作者	Neary, William J.1; Zhao, Fengyue 2; Murphy, Megan C.1; Chen, Yu3,4 ; Liu, Fang 2; Houk, K. N.5; Moore, Jeffrey S.6,7
通讯作者	Neary, William J.; Liu, Fang; Houk, K. N.; Moore, Jeffrey S.
发表日期	2024-05-30
DOI	10.1021/acs.macromol.4c00699
发表期刊	MACROMOLECULES 影响因子和分区
ISSN	0024-9297
EISSN	1520-5835
卷号	57 期号:11
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.
相关链接	[来源记录]
收录类别	SCI ; EI
语种	英语
学校署名	其他
资助项目	Division of Chemistry[CHE-2116298] ; NSF Center for the Chemistry of Molecularly Optimized Networks (MONET)[CHE-2153972]
WOS研究方向	Polymer Science
WOS类目	Polymer Science
WOS记录号	WOS:001236244900001
出版者	AMER CHEMICAL SOC
ESI学科分类	CHEMISTRY
来源库	Web of Science
引用统计	被引频次[WOS]：1
成果类型	期刊论文
条目标识符	http://sustech.caswiz.com/handle/2SGJ60CL/788297
专题	理学院_化学系深圳格拉布斯研究院
作者单位	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
推荐引用方式 GB/T 7714	Neary, William J.,Zhao, Fengyue,Murphy, Megan C.,et al. Substituent Effects on Ring Opening Allene Metathesis: Polymerization Rate Enhancement and Regioregularity[J]. MACROMOLECULES,2024,57(11).
APA	Neary, William J..,Zhao, Fengyue.,Murphy, Megan C..,Chen, Yu.,Liu, Fang.,...&Moore, Jeffrey S..(2024).Substituent Effects on Ring Opening Allene Metathesis: Polymerization Rate Enhancement and Regioregularity.MACROMOLECULES,57(11).
MLA	Neary, William J.,et al."Substituent Effects on Ring Opening Allene Metathesis: Polymerization Rate Enhancement and Regioregularity".MACROMOLECULES 57.11(2024).