N-Substituted Iminocaprolactams as Versatile and Low Cost Ligands in Group 4 Metal Initiators for the Living Coordinative Chain Transfer Polymerization of α-Olefins,Organometallics

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N-Substituted Iminocaprolactams as Versatile and Low Cost Ligands in Group 4 Metal Initiators for the Living Coordinative Chain Transfer Polymerization of α-Olefins
Organometallics ( IF 2.5 ) Pub Date : 2017-10-19 00:00:00 , DOI: 10.1021/acs.organomet.7b00643
Jia Wei ₁ , Leila M. Duman ₁ , Daniel W. Redman ₁ , Brendan L. Yonke ₁ , Peter Y. Zavalij ₁ , Lawrence R. Sita ₁

Affiliation

A new structurally diverse ligand for metal complexes, the (κ²-N,N)-iminocaprolactam group, that can be obtained in large bulk quantities from inexpensive and readily available starting materials, is introduced. In the present report, the ability of this family of ligands to provide a viable substitute for the acyclic amidinate moiety of a class of cationic monocyclopentadienyl, amidinate (CPAM) group 4 metal initiators for the living coordination polymerization (LCP) and living coordinative chain transfer polymerization (LCCTP) of α-olefins is documented through the synthesis of (η⁵-C₅Me₅)Hf[(R)N^imcapN](Me)₂ [R = benzyl (1), CH₂(1-naphthyl) (2), and tert-butyl [C(CH₃)₃] (3)] as preinitiators for the (stereoselective) LCP and LCCTP of propene.

中文翻译：

N-取代的氨基己内酰胺作为α-烯烃活性配位链转移聚合的第4组金属引发剂中的多功能低成本配体

对于金属配合物的新结构不同的配体，所述（κ ² - Ñ，Ñ）-iminocaprolactam组，可在从便宜和容易获得的起始原料大散装量来获得，被引入。在本报告中，该配体家族为活性配位聚合（LCP）和活性配位链转移提供了一类阳离子单环戊二烯基a酰胺（CPAM）4类金属引发剂的无环a酰胺部分的可行替代物的能力α烯烃的聚合（LCCTP）通过的合成记载（η ⁵ -C ₅我₅）的Hf [（R）N ^imcap N]（Me）的₂ [R =苄基（1），CH ₂（1-萘基）（2）和叔丁基[C（CH ₃）₃ ]（3）]作为丙烯（立体选择性）LCP和LCCTP的预引发剂。

更新日期：2017-10-19

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