Structural Insights from        <sup >5959        Co Solid‐State NMR Experiments on Organocobalt(I) Catalysts

Burgess Kevin M. N.; Widdifield Cory M.; Xu Yang; Leroy César; Bryce David L.

摘要

Abstract > A series of fumarate‐based organocobalt(I) [CoCp(CO)(fumarate)] catalysts is synthesized and characterized by X‐ray crystallography, multinuclear ( 13 C and 59 Co) solid‐state NMR spectroscopy, and 59 Co NQR spectroscopy. Given the dearth of 59 Co solid‐state NMR studies on Co I compounds, the present work constitutes the first systematic characterization of the 59 Co electric field gradient and chemical shift tensors for a series of cobalt complexes in this oxidation state. Using X‐ray crystallography, the molecular geometry about the Co I centre is found to be nearly identical in all compounds studied herein. Owing to the 59 Co nucleus’ large chemical shift range, solid‐state NMR experiments are found to be able to detect small structural differences between the individual organocobalt(I) compounds. With the aid of density functional theory calculations on these complexes, it is shown that the 59 Co chemical shift anisotropy and the 59 Co quadrupolar coupling constant are both extremely sensitive gauges of the Fu‐Co‐Cp bond angle, providing a link between these 59 Co NMR observables and the catalysts’ structures. </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> >一系列富马酸富马酸核苷酸（I）[COCP（CO）（富马特）]通过X射线晶体学，多核（ 13-sup> c和 59℃）固态NMR光谱，以及 59 </ sup> co nqr的合成和表征催化剂。光谱学。鉴于CO <SUP> I CO </ SOP>化合物的 59 </ sup> CO固态NMR研究的缺乏研究，本作本作品构成了 59 </ sup> co电气的第一系统表征在该氧化态中的一系列钴络合物的场梯度和化学移位张力。使用X射线晶体术，在本文研究的所有化合物中发现涉及CO <SUP> I </ SUP>中心的分子几何形状几乎相同。由于 59 </ sup> co nucleus的大化学位移范围，发现固态NMR实验能够检测各种有机钴（I）化合物之间的小结构差异。借助于密度函数理论计算这些配合物上，显示 59 </ sup> co化学换档各向异性和 59 </ sup> co quadrupolar耦合常数是极其敏感的仪表FU-CO-CP键合角度，提供这些 59 </ sup> CO NMR观察品和催化剂结构之间的链接。 </ p> </ abstract> </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-16300/'>《Chemphyschem: A European journal of chemical physics and physical chemistry》</a> <b style="margin: 0 2px;">|</b><span>2018年第2期</span><b style="margin: 0 2px;">|</b><span>共10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=Burgess Kevin M. N.&option=202" target="_blank" rel="nofollow">Burgess Kevin M. N.;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Widdifield Cory M.&option=202" target="_blank" rel="nofollow">Widdifield Cory M.;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Xu Yang&option=202" target="_blank" rel="nofollow">Xu Yang;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Leroy César&option=202" target="_blank" rel="nofollow">Leroy César;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Bryce David L.&option=202" target="_blank" rel="nofollow">Bryce David L.;</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>Department of Chemistry and Biomolecular Sciences &</p> <p>Centre for Catalysis Research and InnovationUniversity of Ottawa10 Marie Curie Private Ottawa Ontario K1N 6N5 Canada;</p> <p>Department of Chemistry and Biomolecular Sciences &</p> <p>Centre for Catalysis Research and InnovationUniversity of Ottawa10 Marie Curie Private Ottawa Ontario K1N 6N5 Canada;</p> <p>Department of Chemistry and Biomolecular Sciences &</p> <p>Centre for Catalysis Research and InnovationUniversity of Ottawa10 Marie Curie Private Ottawa Ontario K1N 6N5 Canada;</p> <p>Department of Chemistry and Biomolecular Sciences &</p> <p>Centre for Catalysis Research and InnovationUniversity of Ottawa10 Marie Curie Private Ottawa Ontario K1N 6N5 Canada;</p> <p>Department of Chemistry and Biomolecular Sciences &</p> <p>Centre for Catalysis Research and InnovationUniversity of Ottawa10 Marie Curie Private Ottawa Ontario K1N 6N5 Canada;</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/1186.html" title="物理化学（理论化学）、化学物理学">物理化学（理论化学）、化学物理学;</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=catalysts&option=203" rel="nofollow">catalysts;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=cobalt&option=203" rel="nofollow">cobalt;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=oxidation state&option=203" rel="nofollow">oxidation state;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=quadrupolar coupling&option=203" rel="nofollow">quadrupolar coupling;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=solid-state NMR&option=203" rel="nofollow">solid-state NMR;</a> </p> <div class="translation"> 机译：催化剂;钴;氧化状态;Quadrupolar耦合;固态NMR; </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/0704022115806.html">Structural Insights from <sup >5959 Co Solid‐State NMR Experiments on Organocobalt(I) Catalysts</a> <b>[J]</b> . <span> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Burgess Kevin M. 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Structural Insights from 5959 Co Solid‐State NMR Experiments on Organocobalt(I) Catalysts

摘要

Structural Insights from ^{5959 Co Solid‐State NMR Experiments on Organocobalt(I) Catalysts}