本文主要研究内容
作者王亚空(2019)在《有机碱金属-烷基镁/锌化合物的合成、结构与反应性》一文中研究指出:有机双金属化合物因其独特的协同效应,相较于单金属试剂而言,往往表现出不同于单金属试剂的反应性和选择性,吸引了广大化学工作者的极大兴趣与关注。大量含有碱金属的异核双金属化合物已经被陆续报道,并应用于化学计量反应或者催化反应。其中,有机镁、锌试剂作为常见的有机金属试剂,在诸多基本有机反应中占有重要作用,其温和的亲核性及特殊的官能团耐受性备受瞩目,但其较差的动力学反应性极大地限制了其应用范围。而由碱金属化合物和有机镁、锌试剂形成的异核双金属化合物既可以降低碱金属化合物的碱性,同时提高有机镁、锌试剂的亲核性,广泛应用于金属化反应和卤素金属交换反应中。但迄今为止,该类双金属试剂主要以化学计量反应为主,很少作为催化剂应用于各类有机催化反应。基于课题组的前期工作与广泛的文献调研,本论文的研究目的是通过N,N-双齿吡咯配体与有机碱金属试剂和烷基镁、锌试剂合成系列N,N-双齿吡咯碱金属-烷基镁、锌等双金属化合物,并通过核磁、X-ray单晶衍射表征得到相应的结构信息。并将它们作为催化剂应用于不同醛类化合物之间的交叉偶合Tishchenko反应,高选择性的合成单一酯类化合物。具体研究工作如下:(1)N,N-双齿吡咯配体C4H3NH2-CH2NHtBu)分别与nBuLi,NaH和KH进行碱金属化反应,然后加入二丁基镁反应,获得五个碱金属-烷基镁化合物,[L i2(THF)4Mg{C4H3N(2-CH2NtBu)}2](2a),[Li2(TMEDA)2Mg{C4H3N(2-CH2NtBu)}2](2b),[Na(THF(Et2C)Na{C4H3N2-CH2N(tBu)MgnBu)}2]∞(2c)和[Na(TMEDA)2Na{C4H3N(2-CH2N(tBu)MgnBu)}2](2d),[K(THF)2K{C4H3N(2-CH2N(tBu)MgnBu)}2]∞(2e),其中化合物2a-2d获得单晶结构并经过核磁分析表征。X-ray单晶结构分析显示由于碱金属原子半径的不断增大及其灵活的配位模式,双金属化合物的结构呈现出多样性。将化合物2a-2e用于催化不同醛之间的交叉偶合季先科反应,条件实验表明,化合物2c为催化剂,在无溶剂或甲苯溶剂中可以获得高选择性、高产率的单一酯类化合物。为阐明双金属化合物的协同效应内涵在高选择性交叉偶合季先科反应中的作用提供了实验上的有利证据。(2)同样,以N,N-双齿吡咯配体C4H3H2-CH2NH(tBu)分别与nBuLi,Na H和KH进行碱金属化反应,然后加入二乙基锌反应,在TMEDA或THF存在的条件下得到四个碱金属-烷基锌化合物[Li(TMEDA)2]+[Li{C4H3N(2-CH2N(tBu)ZnC2H5)}2]-(3a),[Na(TMEDA)Na{C4H3N(2-CH2N(tBu)ZnC2H5)}2]∞(3b),[Na(T HF)2Na{C4H3N(2-CH2N(tBu)ZnC2H5)}2]∞(3c)和[K(THF)2{C4H3N(2-CH2N(tBu)Z nC2H5)}2K]∞(3d),化合物3a-3d均获得单晶结构,并经过核磁分析表征。X-ray单晶分析表明,这些化合物显示出从单分子化合物到配位聚合物的结构多样性。该类新型碱金属烷基锌化合物将为含有吡咯基金属配合物的研究提供了新的思路,为双金属化合物的协同效应研究提供了有力支撑。
Abstract
you ji shuang jin shu hua ge wu yin ji du te de xie tong xiao ying ,xiang jiao yu chan jin shu shi ji er yan ,wang wang biao xian chu bu tong yu chan jin shu shi ji de fan ying xing he shua ze xing ,xi yin le an da hua xue gong zuo zhe de ji da xing qu yu guan zhu 。da liang han you jian jin shu de yi he shuang jin shu hua ge wu yi jing bei liu xu bao dao ,bing ying yong yu hua xue ji liang fan ying huo zhe cui hua fan ying 。ji zhong ,you ji mei 、xin shi ji zuo wei chang jian de you ji jin shu shi ji ,zai zhu duo ji ben you ji fan ying zhong zhan you chong yao zuo yong ,ji wen he de qin he xing ji te shu de guan neng tuan nai shou xing bei shou zhu mu ,dan ji jiao cha de dong li xue fan ying xing ji da de xian zhi le ji ying yong fan wei 。er you jian jin shu hua ge wu he you ji mei 、xin shi ji xing cheng de yi he shuang jin shu hua ge wu ji ke yi jiang di jian jin shu hua ge wu de jian xing ,tong shi di gao you ji mei 、xin shi ji de qin he xing ,an fan ying yong yu jin shu hua fan ying he lu su jin shu jiao huan fan ying zhong 。dan qi jin wei zhi ,gai lei shuang jin shu shi ji zhu yao yi hua xue ji liang fan ying wei zhu ,hen shao zuo wei cui hua ji ying yong yu ge lei you ji cui hua fan ying 。ji yu ke ti zu de qian ji gong zuo yu an fan de wen suo diao yan ,ben lun wen de yan jiu mu de shi tong guo N,N-shuang chi bi ge pei ti yu you ji jian jin shu shi ji he wan ji mei 、xin shi ji ge cheng ji lie N,N-shuang chi bi ge jian jin shu -wan ji mei 、xin deng shuang jin shu hua ge wu ,bing tong guo he ci 、X-raychan jing yan she biao zheng de dao xiang ying de jie gou xin xi 。bing jiang ta men zuo wei cui hua ji ying yong yu bu tong quan lei hua ge wu zhi jian de jiao cha ou ge Tishchenkofan ying ,gao shua ze xing de ge cheng chan yi zhi lei hua ge wu 。ju ti yan jiu gong zuo ru xia :(1)N,N-shuang chi bi ge pei ti C4H3NH2-CH2NHtBu)fen bie yu nBuLi,NaHhe KHjin hang jian jin shu hua fan ying ,ran hou jia ru er ding ji mei fan ying ,huo de wu ge jian jin shu -wan ji mei hua ge wu ,[L i2(THF)4Mg{C4H3N(2-CH2NtBu)}2](2a),[Li2(TMEDA)2Mg{C4H3N(2-CH2NtBu)}2](2b),[Na(THF(Et2C)Na{C4H3N2-CH2N(tBu)MgnBu)}2]∞(2c)he [Na(TMEDA)2Na{C4H3N(2-CH2N(tBu)MgnBu)}2](2d),[K(THF)2K{C4H3N(2-CH2N(tBu)MgnBu)}2]∞(2e),ji zhong hua ge wu 2a-2dhuo de chan jing jie gou bing jing guo he ci fen xi biao zheng 。X-raychan jing jie gou fen xi xian shi you yu jian jin shu yuan zi ban jing de bu duan zeng da ji ji ling huo de pei wei mo shi ,shuang jin shu hua ge wu de jie gou cheng xian chu duo yang xing 。jiang hua ge wu 2a-2eyong yu cui hua bu tong quan zhi jian de jiao cha ou ge ji xian ke fan ying ,tiao jian shi yan biao ming ,hua ge wu 2cwei cui hua ji ,zai mo rong ji huo jia ben rong ji zhong ke yi huo de gao shua ze xing 、gao chan lv de chan yi zhi lei hua ge wu 。wei chan ming shuang jin shu hua ge wu de xie tong xiao ying nei han zai gao shua ze xing jiao cha ou ge ji xian ke fan ying zhong de zuo yong di gong le shi yan shang de you li zheng ju 。(2)tong yang ,yi N,N-shuang chi bi ge pei ti C4H3H2-CH2NH(tBu)fen bie yu nBuLi,Na Hhe KHjin hang jian jin shu hua fan ying ,ran hou jia ru er yi ji xin fan ying ,zai TMEDAhuo THFcun zai de tiao jian xia de dao si ge jian jin shu -wan ji xin hua ge wu [Li(TMEDA)2]+[Li{C4H3N(2-CH2N(tBu)ZnC2H5)}2]-(3a),[Na(TMEDA)Na{C4H3N(2-CH2N(tBu)ZnC2H5)}2]∞(3b),[Na(T HF)2Na{C4H3N(2-CH2N(tBu)ZnC2H5)}2]∞(3c)he [K(THF)2{C4H3N(2-CH2N(tBu)Z nC2H5)}2K]∞(3d),hua ge wu 3a-3djun huo de chan jing jie gou ,bing jing guo he ci fen xi biao zheng 。X-raychan jing fen xi biao ming ,zhe xie hua ge wu xian shi chu cong chan fen zi hua ge wu dao pei wei ju ge wu de jie gou duo yang xing 。gai lei xin xing jian jin shu wan ji xin hua ge wu jiang wei han you bi ge ji jin shu pei ge wu de yan jiu di gong le xin de sai lu ,wei shuang jin shu hua ge wu de xie tong xiao ying yan jiu di gong le you li zhi cheng 。
论文参考文献
论文详细介绍
论文作者分别是来自山西大学的王亚空,发表于刊物山西大学2019-11-12论文,是一篇关于吡咯配体论文,有机双金属化合物论文,结构论文,催化论文,交叉偶合季先科反应论文,山西大学2019-11-12论文的文章。本文可供学术参考使用,各位学者可以免费参考阅读下载,文章观点不代表本站观点,资料来自山西大学2019-11-12论文网站,若本站收录的文献无意侵犯了您的著作版权,请联系我们删除。
标签:吡咯配体论文; 有机双金属化合物论文; 结构论文; 催化论文; 交叉偶合季先科反应论文; 山西大学2019-11-12论文;