Ligand Effects on the Electronic Structure of Heteroleptic Antimony‐Centered Radicals

Helling Christoph; Cutsail George E.; Weinert Hanns; W?lper Christoph; Schulz Stephan

摘要

Abstract > We report on the structures of three unprecedented heteroleptic Sb‐centered radicals [L(Cl)Ga](R)Sb . ( 2‐R , R=B[N(Dip)CH] <sub>2</sub> 2‐B , 2,6‐Mes <sub>2</sub> C <sub>6</sub> H <sub>3</sub> 2‐C , N(SiMe <sub>3</sub> )Dip 2‐N ) stabilized by one electropositive metal fragment [L(Cl)Ga] (L=HC[C(Me)N(Dip)] <sub>2</sub> , Dip=2,6‐ i ‐Pr <sub>2</sub> C <sub>6</sub> H <sub>3</sub> ) and one bulky B‐ ( 2‐B ), C‐ ( 2‐C ), or N‐based ( 2‐N ) substituent. Compounds 2‐R are predominantly metal‐centered radicals. Their electronic properties are largely influenced by the electronic nature of the ligands R, and significant delocalization of unpaired‐spin density onto the ligands was observed in 2‐B and 2‐N . Cyclic voltammetry (CV) studies showed that 2‐B undergoes a quasi‐reversible one‐electron reduction, which was confirmed by the synthesis of [K([2.2.2]crypt)][L(Cl)GaSbB[N(Dip)CH] <sub>2</sub> ] ([K([2.2.2]crypt)][ 2‐B ]) containing the stibanyl anion [ 2‐B ] ? , which was shown to possess significant Sb?B multiple‐bonding character. </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> > 我们报告了三个前所未有的异常的异基团的基团[L（Cl）Ga]（R）Sb的结构。</ sup> （ 2-r </ b> ，r = b [n（dip）ch] <sub> 2 </ sub> 2-b </ b> ，2,6米 <sub> 2 </ sub> C <sub> 6 </ sub> H <sub> 3 </ sub> 2-c </ b> ，n（Sime <sub> 3 </ sub> ）蘸 2-n </ b> ）通过一种电动金属片段稳定[L（CL）Ga]（L = HC [C（ME）N（DIP）] <sub> 2 </ sub> ，dip = 2,6- 我</ i> -pr. <sub> 2 </ sub> C <sub> 6 </ sub> H <sub> 3 </ sub> ）和一个笨重的b-（ 2-b </ b> ）， C- （ 2-c </ b> ）或基于n（ 2-n </ b> ）取代基。化合物 2-r </ b> 主要是金属居中的基础。它们的电子性质主要受到配体R的电子性质的影响，并且观察到在配体上的未配对旋转密度的显着临近临床化 2-b </ b> 和 2-n </ b> 。循环伏安法（CV）研究表明 2-b </ b> 经历一种准可逆的单电子减少，其通过合成[k（[2.2.2隐隐）] [L（CL）Gasbb [n（dip）ch]来证实 <sub> 2 </ sub> ]（[k（[2.2.2] crypt）] [ 2-b </ b> ]）含有体内阴离子[ 2-b </ b> ] ？</ sup> ，这被证明具有显着的SB？B多键合性。 </ 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>2020年第19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"> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Helling Christoph&option=202" target="_blank" rel="nofollow">Helling Christoph;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Cutsail George E.&option=202" target="_blank" rel="nofollow">Cutsail George E.;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Weinert Hanns&option=202" target="_blank" rel="nofollow">Weinert Hanns;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=W?lper Christoph&option=202" target="_blank" rel="nofollow">W?lper Christoph;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Schulz Stephan&option=202" target="_blank" rel="nofollow">Schulz Stephan;</a> </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"> <p>Institute for Inorganic Chemistry and Center for Nanointegration Duisburg-Essen (Cenide)University of Duisburg-EssenUniversit?tsstra?e 5–7 45117 Essen Germany;</p> <p>Max Planck Institute for Chemical Energy Conversion (CEC)Stiftstra?e 34–36 45470 Mülheim an der Ruhr Germany;</p> <p>Institute for Inorganic Chemistry and Center for Nanointegration Duisburg-Essen (Cenide)University of Duisburg-EssenUniversit?tsstra?e 5–7 45117 Essen Germany;</p> <p>Institute for Inorganic Chemistry and Center for Nanointegration Duisburg-Essen (Cenide)University of Duisburg-EssenUniversit?tsstra?e 5–7 45117 Essen Germany;</p> <p>Institute for Inorganic Chemistry and Center for Nanointegration Duisburg-Essen (Cenide)University of Duisburg-EssenUniversit?tsstra?e 5–7 45117 Essen Germany;</p> </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=antimony&option=203" rel="nofollow">antimony;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=EPR spectroscopy&option=203" rel="nofollow">EPR spectroscopy;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=main-group elements&option=203" rel="nofollow">main-group elements;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=radicals&option=203" rel="nofollow">radicals;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=X-ray diffraction&option=203" rel="nofollow">X-ray diffraction;</a> </p> <div class="translation"> 机译：锑;EPR光谱;主要群体元素;自由基;X射线衍射; </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/0704028161926.html">Ligand Effects on the Electronic Structure of Heteroleptic Antimony‐Centered Radicals</a> <b>[J]</b> . <span> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Helling Christoph&option=202" target="_blank" rel="nofollow" class="tuijian_auth tuijian_authcolor">Helling Christoph,</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Cutsail George E.&option=202" target="_blank" rel="nofollow" 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