Element–Element Bond Formation upon Oxidation and Reduction

Piesch Martin; Gra?l Christian; Scheer Manfred

摘要

Abstract > The redox chemistry of [(Cp′′′Co) <sub>2</sub> (μ,η 2 :η 2 ‐E <sub>2</sub> ) <sub>2</sub> ] (E=P ( 1 ), As ( 2 ); Cp′′′=1,2,4‐tri( tert ‐butyl)cyclopentadienyl) was investigated. Both compounds can be oxidized and reduced twice. That way, the monocations [(Cp′′′Co) <sub>2</sub> (μ,η 4 :η 4 ‐E <sub>4</sub> )][X] (E=P, X=BF <sub>4</sub> ( 3?a ), [FAl] ( 3?b ); E=As, X=BF <sub>4</sub> ( 4?a ), [FAl] ( 4?b )), the dications [(Cp′′′Co) <sub>2</sub> (μ,η 4 :η 4 ‐E <sub>4</sub> )][TEF] <sub>2</sub> (E=P ( 5 ), As ( 6 )), and the monoanions [K(18‐c‐6)(dme) <sub>2</sub> ][(Cp′′′Co) <sub>2</sub> (μ,η 4 :η 4 ‐E <sub>4</sub> )] (E=P ( 7 ), As ( 8 )) were isolated. Further reduction of 7 leads to the dianionic complex [K(18‐c‐6)(dme) <sub>2</sub> ][K(18‐c‐6)][(Cp′′′Co) <sub>2</sub> (μ,η 3 :η 3 ‐P <sub>4</sub> )] ( 9 ), in which the cyclo‐P <sub>4</sub> ligand has rearranged to a chain‐like P <sub>4</sub> ligand. Further reduction of 8 can be achieved with an excess of potassium under the formation of [K(dme) <sub>4</sub> ][(Cp′′′Co) <sub>2</sub> (μ,η 3 :η 3 ‐As <sub>3</sub> )] ( 10 ) and the elimination of an As <sub>1</sub> unit. Compound 10 represents the first example of an allylic As <sub>3</sub> ligand incorporated into a triple‐decker complex. </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> > [（CP''CO）的氧化还原化学 <sub> 2 </ sub> （μ，η 2 </ sup> ：η. 2 </ sup> -e. <sub> 2 </ sub> 的） <sub> 2 </ sub> ]（e = p（ 1 </ b> ），作为（ 2 </ b> ）; cp''= 1,2,4-tri（ tert </ i> 对丁二丁二烯基）进行了研究。两种化合物都可以氧化并减少两次。这样，单体化[（CP''CO） <sub> 2 </ sub> （μ，η 4 </ sup> ：η. 4 </ sup> -e. <sub> 4 </ sub> ）[x]（e = p，x = bf <sub> 4 </ sub> （ 3？a </ b> ），[FAL]（ 3？b </ b> ）; e = AS，X = BF <sub> 4 </ sub> （ 4？a </ b> ），[FAL]（ 4？b </ b> ）），DIMES [（CP''CO） <sub> 2 </ sub> （μ，η 4 </ sup> ：η. 4 </ sup> -e. <sub> 4 </ sub> ）] [TEF] <sub> 2 </ sub> （e = p（ 5 </ b> ），作为（ 6 </ b> ））和单体[K（18-C-6）（DME） <sub> 2 </ sub> ] [（CP''CO） <sub> 2 </ sub> （μ，η 4 </ sup> ：η. 4 </ sup> -e. <sub> 4 </ sub> ）（e = p（ 7 </ b> ），作为（ 8 </ b> ））被孤立。进一步减少 7 </ b> 导致Dianionic Complex [K（18-C-6）（DME） <sub> 2 </ sub> ] [K（18-C-6）] [（CP''CO） <sub> 2 </ sub> （μ，η 3 </ sup> ：η. 3 </ sup> -P. <sub> 4 </ sub> ）]（ 9 </ b> ），其中cyclo-p <sub> 4 </ sub> 配体重新排列到链状p <sub> 4 </ sub> 配体。进一步减少 8 </ b> 通过在形成[K（DME）的形成下有过量的钾可以实现 <sub> 4 </ sub> ] [（CP''CO） <sub> 2 </ sub> （μ，η 3 </ sup> ：η. 3 </ sup> -作为 <sub> 3 </ sub> ）]（ 10 </ b> ）并消除AS <sub> 1 </ sub> 单元。化合物 10 </ b> 代表烯丙基的第一例 <sub> 3 </ sub> 配体掺入三层复合物中。 </ 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18期</span><b style="margin: 0 2px;">|</b><span>共7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=Piesch Martin&option=202" target="_blank" rel="nofollow">Piesch Martin;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Gra?l Christian&option=202" target="_blank" rel="nofollow">Gra?l Christian;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Scheer Manfred&option=202" target="_blank" rel="nofollow">Scheer Manfred;</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>Institut für Anorganische ChemieUniversit?t Regensburg93040 Regensburg Germany;</p> <p>Institut für Anorganische ChemieUniversit?t Regensburg93040 Regensburg Germany;</p> <p>Institut für Anorganische ChemieUniversit?t Regensburg93040 Regensburg 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=arsenic&option=203" rel="nofollow">arsenic;</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=cyclic voltammetry&option=203" rel="nofollow">cyclic voltammetry;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=phosphorus&option=203" rel="nofollow">phosphorus;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=redox chemistry&option=203" rel="nofollow">redox chemistry;</a> </p> <div class="translation"> 机译：砷;钴;循环伏安法;磷;氧化还原化学; 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class="enjiyixqcontent" href="/academic-journal-cn_china-tungsten-industry_thesis/0201293790441.html">包含铌及钨元素中的至少一种以及锰、钒及铜元素的催化活性多元素氧化物材料的制备</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> <span> <a href="/journal-cn-8036/" target="_blank" rel="nofollow" class="tuijian_authcolor"> . 中国钨业 </a> </span> <span> . 2009</span><span>,第3期</span> </span> </div> </li> <li> <div> <b>6. </b><a class="enjiyixqcontent" href="/academic-conference-cn_meeting-37685_thesis/020221612518.html">元素硫的应用和生产——兼述碳和一氧化碳还原二氧化硫制元素硫</a> <b>[C]</b> <span> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=彭克诚&option=202" target="_blank" rel="nofollow" class="tuijian_auth tuijian_authcolor"> . 彭克诚</a> <span> <a href="/conference-cn-37685/" target="_blank" rel="nofollow" class="tuijian_authcolor"> . 1987年全国硫酸工业技术交流会 </a> <span> <span> . 1987</span> </span> </div> </li> <li> <div> <b>7. </b><a class="enjiyixqcontent" href="/academic-degree-domestic_mphd_thesis/020312128958.html">稀土金属La元素对C-C键和C-H键活化影响的理论研究</a> <b>[A] </b> <span> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=王雅&option=202" target="_blank" rel="nofollow" class="tuijian_auth tuijian_authcolor"> . 王雅</a> <span> . 2016</span> </span> </div> </li> </ul> <ul style="display: none;"> <li> <div> <b>1. </b><a class="enjiyixqcontent" href="/patent-detail/061201458998.html">某些化学元素在用于抑制含元素钼和元素锆的水溶液中含钼酸锆沉淀物形成的应用及一种用于再加工含有元素钼和元素锆的用过的燃料的方法</a> <b>[P]</b> . <span> 中国专利： CN102648497B </span> <span> . 2014.10.15</span> </div> </li> <li> <div> <b>2. </b><a class="enjiyixqcontent" href="/patent-detail/06120111812456.html">镧系元素化合物、含镧系元素薄膜及使用该镧系元素化合物形成含镧系元素薄膜</a> <b>[P]</b> . <span> 中国专利： CN111770927A </span> <span> . 2020-10-13</span> </div> </li> <li> <div> <b>3. </b><a class="enjiyixqcontent" href="/patent-detail/06130424325344.html">Method and device for recycling carbon dioxide for producing the elements, comprises breaking atomic bond of carbon dioxide by special energy probe and separately collecting the elements with or without the catalyst</a> <b>[P]</b> . <span> 外国专利：  DE102009021955A1 </span> <span> . 2010-11-25</span> </div> <p class="zwjiyix translation" style="max-width: initial;height: auto;word-break: break-all;white-space: initial;text-overflow: initial;overflow: initial;"> <span>机译：回收二氧化碳以生产元素的方法和装置，包括通过特殊的能量探针破坏二氧化碳的原子键，并在有或没有催化剂的情况下分别收集元素 </span> </p> </li> <li> <div> <b>4. </b><a class="enjiyixqcontent" href="/patent-detail/06130443703109.html">Device for reducing formation of nitrogen oxides in Internal Combustion engines comprises valve arranged between engine and two parallel storage elements for nitrogen oxides, and further valve connected to storage elements</a> <b>[P]</b> . <span> 外国专利：  DE10148911A1 </span> <span> . 2003-04-10</span> </div> <p class="zwjiyix translation" style="max-width: initial;height: auto;word-break: break-all;white-space: initial;text-overflow: initial;overflow: initial;"> <span>机译：用于减少内燃机中氮氧化物形成的装置包括：阀，其布置在发动机与两个平行的氮氧化物存储元件之间;以及另外的与存储元件连接的阀 </span> </p> </li> <li> <div> <b>5. </b><a class="enjiyixqcontent" href="/patent-detail/06130439086915.html">Barcode arrangement for storing medical information comprises barcode elements having identification elements for testing the bond of the barcode elements using a barcode laser</a> <b>[P]</b> . <span> 外国专利：  DE10341313A1 </span> <span> . 2005-04-07</span> </div> <p class="zwjiyix translation" style="max-width: initial;height: auto;word-break: break-all;white-space: initial;text-overflow: initial;overflow: initial;"> <span>机译：用于存储医疗信息的条形码装置包括具有识别元件的条形码元件，该识别元件用于使用条形码激光器测试条形码元件的结合 </span> </p> </li> </ul> </div> </div> </div> <div class="theme cardcommon" style="overflow: auto;display:none"> <h3 class="all_title" id="enpatent55">相关主题</h3> <ul id="subject"> </ul> </div> </div> </div> </div> <div class="right rightcon"> <div class="details_img cardcommon 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