CCC型钳形铑配合物的反应性  

The reactivities of novel rhodium CCC-type pincer complexes

作　　者：林剑锋 罗明[1] 夏海平 Jianfeng Lin;Ming Luo;Haiping Xia(Shenzhen Grubbs Institute,Guangdong Provincial Key Laboratory of Catalysis,Department of Chemistry,Southern University of Science and Technology,Shenzhen 518055,China;Department of Chemistry,Xiamen University,Xiamen 361005,China)

机构地区：[1]南方科技大学化学系,广东省催化化学重点实验室,深圳格拉布斯研究院,深圳518055 [2]厦门大学化学系,厦门361005

出　　处：《科学通报》2021年第25期3333-3341,共9页Chinese Science Bulletin

基　　金：国家自然科学基金(U1705254,21931002);广东省催化化学重点实验室基金(2020B121201002);深圳市科技创新委员会基础研究重点项目(JCYJ20200109140812302)资助。

摘　　要：钳形金属配合物因其独特的结构、性质和应用引起了化学家的广泛关注.然而该类配合物大部分都是以2~3个杂原子(基团)与金属原子配位.只有极少数例子同时具有3个碳原子与金属配位(CCC钳形金属配合物).这是由于该类配合物具有3个金属-碳共价键,通常会具有较高的反应活性.我们对一类新颖的CCC型钳形铑配合物:铑碳龙配合物的反应性开展了深入的研究,发现这类铑配合物能与二氧化锰反应,得到氧化产物和开环产物;也能与叠氮三甲基硅烷和二苯基膦发生亲核反应,实现了氮和磷对铑卡宾的插入反应,分别得到氮、磷插入到金属杂环中的扩环产物:CCN型和CCP型铑配合物.这些研究拓展了碳基钳形金属配合物(以碳为主要配位原子的螯合物)的反应化学,并为碳基铑配合物在催化上的应用打下基础.Pincer complexes have attracted chemists’attention because of their unique structures,properties,and catalytic applications.Among these pincer complexes,most of them are based on heteroatoms,such as nitrogen,oxygen,phosphorus,sulfur and so on.Few examples that three carbon atoms coordinate to metal(CCC-type pincer)have been reported due to their highly active reactivities.Recently,our group reported a series of novel metal bridgehead fused-ring organometallics,named carbolong complexes.Carbolong complexes are special pincer complexes which are metal bridgehead polycyclic frameworks featuring a conjugate carbon chain(at least 7 carbons and we call these carbon chains carbolong ligand)coordinated to a metal atom via at least three metal-carbonσbonds and note that the d orbital of metal atom in cooperation withπconjugation is a particular characteristic in carbolong complexes.In cooperation with metal,carbolong complexes exhibit numerous distinctive properties different form typical aromatics,such as mixed aromaticity,broad absorption from the UV to the visible and near-infrared region,and excellent photothermal effects,indicating their potential applications in materials science and biomedicine.The reported carbolong complexes were mostly based on osmium,limited their application development.Thanks to the efficient method we developed very recently,the rhodium carbolong complexes,rhodapentalenes were synthesized successfully,which displayed unique intrinsic aromaticity and diverse reactivities.As a novel CCC-type rhodium pincer complexes,the reactivities of rhodapentalenes were rarely investigated.In this report,we investigated the reactivities of two novel rhodium CCC-type pincer complexes.The results showed rhodium carbolong complex 1 could be oxidized by activated Mn O2 and led to complexes 3 and 4,which were confirmed by NMR spectra and single crystal X-ray analysis.Complex 3 was an oxidation product and originated from the oxidation of hydroxy in CCC-type pincer ligand of complex1.However,complex 4 formed

关 键 词：CCC型钳形配合物 碳龙化学 开环反应 扩环反应 铑配合物 

分 类 号：O641.4[理学—物理化学]