The Forgotten Nitroaromatic Phosphines as Weakly Donating P‐ligands: An <i xmlns='http://www.wiley.com/namespaces/wiley'>NN ‐Aryl <b xmlns='http://www.wiley.com/namespaces/wiley'>‐benzimidazolyl Series in RhCl(CO) Complexes‐benzimidazolyl Series in RhCl(CO) Complexes

Zhu Chongwei; Gras Emmanuel; Duhayon Carine; Lacassin Francis; Cui Xiuling; Chauvin Remi

摘要

Abstract > The coordination chemistry of a priori weakly σ ‐donating nitroaromatic phosphines is addressed through a series of nitro‐substituted ( N ‐phenyl‐benzimidazol‐1‐yl)diphenylphosphines in Rh I complexes. From a set of seven such phosphines L=L <sub>xyz</sub> (′) ( x , y , z =0 or 1=number of NO <sub>2</sub> substituents at the 5, 6 and N‐Ph para positions, respectively), including the non‐nitrated parent L <sub>000</sub> and its dicationic N‐methyl counterpart L <sub>000</sub> ′, three LRhCl(COD) and seven L <sub>2</sub> RhCl(CO) complexes have been obtained in 72–95?% yield. Despite of a cis orientation of the L and CO ligands, the C=O IR stretching frequency ν <sub>CO</sub> varies in the expected sense, from 1967±1?cm ?1 for L <sub>xy0</sub> to 1978±1?cm ?1 for L <sub>xy1</sub> , and 2005?cm ?1 for L <sub>000</sub> ′. The 103 Rh NMR chemical shift δ <sub>Rh</sub> varies from ?288?ppm for L <sub>000</sub> to ?316±1?ppm for L <sub>10z</sub> or L <sub>01z</sub> , and ?436?ppm for L <sub>000</sub> ′. The ν <sub>CO</sub> and δ <sub>Rh</sub> probes thus reveal moderate but systematic variations, and act as “orthogonal” spectroscopic indicators of the presence of nitro groups on the N‐Ph group and the benzimidazole core, respectively. For the dicationic ligand L <sub>000</sub> ′, a tight electrostatic sandwiching of the Rh‐Cl bond by the benzimidazole moities is evidenced by X‐ray crystallography (RhCl δ ? ???CN <sub>2</sub> + ≈3.01??). Along with the LRhCl(CO) complexes, dinuclear side‐products (μ‐CO)(RhClL) <sub>2</sub> were also obtained in low spectroscopic yield: for the dinitro ligand L=L <sub>011</sub> , a unique 1:6.7 clathrate structure, with dichloromethane as solvate, is also revealed by X‐ray crystallography. </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 XMLNS =“http://www.wiley.com/namespaces/wiley”type =“main”xml：lang =“en”> <title type =“main”>抽象</ title> >协调通过一系列硝基取代（ N </ I> -phenyl-Benzimidazol-1-苯并咪唑-1-苯基 - 苯并咪唑-1-苯基-Benzimidazol-1-苯并咪唑-1-苯基 - 苯并咪唑-1-苯基 - 苯并咪唑-1-基）二苯基膦，在RH 中致死硝基芳族磷酸酯的化学方法我</ sup>复合物。从一组七种这样的磷酸盐L = L <sub> XYZ </ sub> （'）</ sup>（ x </ i>，<i </ i>， Z </ i> = 0或1 =分别为5,6和N-pH的N-PH和N-pH <I> PARA的含量的NO <sub> 2 </ sub>取代基的数量，包括非氮化父母L <sub> 000 </ sub>及其直接N-甲基对应L <sub> 000 </ sub>'，三lrhcl（cod）和7 l <sub> 2 </ sub> rhcl（co）复合物获得72-95次收率。尽管L和Co配体的升序 CIS，C = O IR拉伸频率ν</ i> <sub> co </ sub>在预期的意义上变化，从1967年起对于L <sub> xy0 </ sub>至1978±1？cm 1 </ sup>对于L <sub> xy1 </ sub>，以及L <sub> xy1 </ sub>的±1？cm ？1 </ sup>。 2005？cm ？1 000 </ sub>'。 103 </ sup> rh NMR化学换档δ</ i> <sub> Rh </ sub>从Δ288变化l <sub> 000 </ sub>到？316±1 ？L <sub> 10z </ sub>或l <sub> 01z </ sub>的ppm，以及l <sub> 000 </ sub>'的436.ppm。 ν</ i> <sub> co </ sub>和δ</ i> <sub> rh </ sub>探针，从而揭示了中等但系统的变化，并充当“正交”光谱指标分别在N-pH基团和苯并咪唑核对硝基的存在。对于DICTIXIC配体L <SUB> 000 </ sub>'，通过X射线晶体学（RHCL <SUP> <I>δ）证明了苯并咪唑薄荷的rH-Cl键的紧密静电夹选（RHCL Δ）。 </ sup> ??? cn <sub> 2 </ sub> + </ sup>≈3.01??）。与LRHCl（CO）配合物一起，在低光谱产率下也获得了二核侧产物（μ-CO）（μ-CO）（rHCL1）<亚/亚>：对于DINITRO配体L = L <SUB> 011 </ Sub>，X射线晶体术还揭示了X射线晶体的唯一1：6.7克拉静脉结构，其作为溶剂化物。 </ 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-16161/'>《Chemistry, an Asian journal》</a> <b style="margin: 0 2px;">|</b><span>2017年第21期</span><b style="margin: 0 2px;">|</b><span>共12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=Zhu Chongwei&option=202" target="_blank" rel="nofollow">Zhu Chongwei;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Gras Emmanuel&option=202" target="_blank" rel="nofollow">Gras Emmanuel;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Duhayon Carine&option=202" target="_blank" rel="nofollow">Duhayon Carine;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Lacassin Francis&option=202" target="_blank" rel="nofollow">Lacassin Francis;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Cui Xiuling&option=202" target="_blank" rel="nofollow">Cui Xiuling;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Chauvin Remi&option=202" target="_blank" rel="nofollow">Chauvin Remi;</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>CNRSLCC (Laboratoire de Chimie de Coordination)205 route de Narbonne BP44099 31077 Toulouse Cedex 4 France;</p> <p>CNRSLCC (Laboratoire de Chimie de Coordination)205 route de Narbonne BP44099 31077 Toulouse Cedex 4 France;</p> <p>CNRSLCC (Laboratoire de Chimie de Coordination)205 route de Narbonne BP44099 31077 Toulouse Cedex 4 France;</p> <p>CNRSLCC (Laboratoire de Chimie de Coordination)205 route de Narbonne BP44099 31077 Toulouse Cedex 4 France;</p> <p>Engineering Research Center of Molecular Medicine Ministry of Education Key Laboratory of Xiamen Marine and Gene Drugs Institutes of Molecular Medicine and School of Biomedical SciencesHuaqiao UniversityXiamen 361021 P.R. China;</p> <p>CNRSLCC (Laboratoire de Chimie de Coordination)205 route de Narbonne BP44099 31077 Toulouse Cedex 4 France;</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/159.html" title="化学">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=coordination bond&option=203" rel="nofollow">coordination bond;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=nitroaromatic chemistry&option=203" rel="nofollow">nitroaromatic chemistry;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=nitroarylphosphines&option=203" rel="nofollow">nitroarylphosphines;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=P ligands&option=203" rel="nofollow">P ligands;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=phosphines&option=203" rel="nofollow">phosphines;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=rhodium carbonyl complexes&option=203" rel="nofollow">rhodium carbonyl complexes;</a> </p> <div class="translation"> 机译：协调键;硝基芳族化学;硝基膦;P配体;磷酸盐;铑羰基络合物; </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> </ul> </div> <div class="similarity_details"> <ul > <li> <div> <b>1. </b><a class="enjiyixqcontent" href="/journal-foreign-detail/0704022087079.html">The Forgotten Nitroaromatic Phosphines as Weakly Donating P‐ligands: An <i xmlns="http://www.wiley.com/namespaces/wiley">NN ‐Aryl <b xmlns="http://www.wiley.com/namespaces/wiley">‐benzimidazolyl Series in RhCl(CO) Complexes‐benzimidazolyl Series in RhCl(CO) Complexes</a> <b>[J]</b> . <span> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Zhu Chongwei&option=202" target="_blank" rel="nofollow" class="tuijian_auth tuijian_authcolor">Zhu Chongwei,</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Gras Emmanuel&option=202" target="_blank" rel="nofollow" class="tuijian_auth tuijian_authcolor">Gras Emmanuel,</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Duhayon Carine&option=202" target="_blank" rel="nofollow" class="tuijian_auth tuijian_authcolor">Duhayon Carine,</a> <a href="/journal-foreign-16161/" target="_blank" rel="nofollow" class="tuijian_authcolor">Chemistry, an Asian journal .</a> <span>2017</span><span>,第21期</span> </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：被遗忘的硝基族膦酸弱捐赠p-ligands：一个<i xmlns =“http://www.wiley.com/namespaces/wiley”> n </ i> n-art <b xmlns =“http：// www .wiley.com / namespaces / wiley“> - rhCl（CO）复合物中的苯并咪唑酯系列</ b> -benzimidazolyl系列rhCl（CO）复合物</span> </p> </li> <li> <div> <b>2. </b><a class="enjiyixqcontent" href="/journal-foreign-detail/0704022086561.html">Inside Cover: Synthesis and Structure of <i xmlns="http://www.wiley.com/namespaces/wiley">NN , <i xmlns="http://www.wiley.com/namespaces/wiley">NN ‐Dinitroamidoborane Complexes (Chem. 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The Forgotten Nitroaromatic Phosphines as Weakly Donating P‐ligands: An NN ‐Aryl ‐benzimidazolyl Series in RhCl(CO) Complexes‐benzimidazolyl Series in RhCl(CO) Complexes

摘要