Unique Bora[1]ferrocenophanes with Sterically Protected Boron: A?Potential Gateway to Helical Polyferrocenes

摘要

Abstract > Silicon‐bridged [1]ferrocenophanes are a versatile class of monomers to obtain well‐defined metallopolymers, however, their boron‐bridged analogues are far less utilized despite being significantly higher strained. We assumed that the reactivity of known bora[1]ferrocenophanes towards ring‐opening polymerization is hampered by π‐donating R <sub>2</sub> N groups at the bridging boron atom and therefore prepared the first bora[1]ferrocenophanes lacking such electronic stabilization. The new, isolated ferrocenophane with a 2,4,6‐triisopropylphenyl group attached to the bridging boron atom exhibits the most tilted Cp rings among all isolated strained sandwich compounds [α(DFT)=33.3°] with a measured record value of the bathochromic shift ( λ <sub>max</sub> =516?nm). Attempts to purify the mesityl analogue by vacuum sublimation transformed this monomer to a purple‐colored polymer that resulted in Cotton effects in circular dichroism spectroscopy. DFT calculations revealed a left‐handed helical structure for this polymer. This is the first evidence for a polyferrocene with a chiral secondary structure. </abstract> </span> <span class="z_kbtn z_kbtnclass hoverxs" style="display: none;">展开▼</span> </div> <div class="translation abstracttxt"> <span class="zhankaihshouqi fivelineshidden" id="abstract"> <span>机译：</span><Abstract Type =“Main”XML：Lang =“en”> <标题类型=“main”>抽象</ title> > 硅桥接[1]亚铁酰亚胺是一种多种单体的单体，以获得良好定义的金属聚合体，然而，尽管紧张性显着更高，但它们的硼桥接类似物的使用远小得多。我们认为，通过π-捐的R阻碍了已知的BoroCenophan朝向开环聚合的反应性 <sub> 2 </ sub> 在桥接硼原子处的n组，因此制备了第一硼[1]缺乏这种电子稳定的硼罗基球。具有2,4,6-三异丙基苯基与桥接硼原子附着的新的分离的二甲苯胺在所有隔离的应变夹层化合物[α（DFT）= 33.3°]中具有最多倾斜的Cp环，其测量的碱基转移（ λ</ i> <sub> max </ sub> = 516？nm）。试图通过真空升华净化β-肌肉类体，使该单体转化为紫色聚合物，导致圆形二色性光谱中的棉花作用。 DFT计算揭示了该聚合物的左手螺旋结构。这是具有手性二级结构的聚丙烯的第一种证据。 </ p> </摘要> </span> <span class="z_kbtn z_kbtnclass hoverxs" style="display: none;">展开▼</span> </div> </div> <div class="record"> <h2 class="all_title" id="enpatent33" >著录项</h2> <ul> <li> <span class="lefttit">来源</span> <div style="width: 86%;vertical-align: text-top;display: inline-block;"> <a href='/journal-foreign-19011/'>《Angewandte Chemie》</a> <b style="margin: 0 2px;">|</b><span>2019年第46期</span><b style="margin: 0 2px;">|</b><span>共8页</span> </div> </li> <li> <div class="author"> <span class="lefttit">作者</span> <p id="fAuthorthree" class="threelineshidden zhankaihshouqi"> </p> <span class="z_kbtnclass z_kbtnclassall hoverxs" id="zkzz" style="display: none;">展开▼</span> </div> </li> <li> <div style="display: flex;"> <span class="lefttit">作者单位</span> <div style="position: relative;margin-left: 3px;max-width: 639px;"> <div class="threelineshidden zhankaihshouqi" id="fOrgthree"> </div> <span class="z_kbtnclass z_kbtnclassall hoverxs" id="zhdw" style="display: none;">展开▼</span> </div> </div> </li> <li > <span class="lefttit">收录信息</span> <span style="width: 86%;vertical-align: text-top;display: inline-block;"></span> </li> <li> <span class="lefttit">原文格式</span> <span>PDF</span> </li> <li> <span class="lefttit">正文语种</span> <span>eng</span> </li> <li> <span class="lefttit">中图分类</span> <span><a href="https://www.zhangqiaokeyan.com/clc/1188.html" title="应用化学">应用化学;</a></span> </li> <li class="antistop"> <span class="lefttit">关键词</span> <p style="width: 86%;vertical-align: text-top;"> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=boron&option=203" rel="nofollow">boron;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=chirality&option=203" rel="nofollow">chirality;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=helical structures&option=203" rel="nofollow">helical structures;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=ring-opening polymerization&option=203" rel="nofollow">ring-opening polymerization;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=strained molecule&option=203" rel="nofollow">strained molecule;</a> </p> <div class="translation"> 机译：硼;手性;螺旋结构;开环聚合;应变分子; </div> </li> </ul> </div> </div> <div class="literature cardcommon"> <div class="similarity "> <h3 class="all_title" id="enpatent66">相似文献</h3> <div class="similaritytab clearfix"> <ul> <li class="active" >外文文献</li> <li >中文文献</li> <li >专利</li> </ul> </div> <div class="similarity_details"> <ul > <li> <div> <b>1. </b><a class="enjiyixqcontent" href="/journal-foreign-detail/0704028163836.html">Unique Bora[1]ferrocenophanes with Sterically Protected Boron: A?Potential Gateway to Helical Polyferrocenes</a> <b>[J]</b> . <span> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=&option=202" target="_blank" rel="nofollow" class="tuijian_auth tuijian_authcolor"> </a> <a href="/journal-foreign-19011/" target="_blank" rel="nofollow" class="tuijian_authcolor">Angewandte Chemie .</a> <span>2019</span><span>,第46期</span> </span> </div> <p class="zwjiyix translation" style="max-width: initial;height: auto;word-break: 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