摘要
2014年,我们设计合成了一类结构独特的螺环稠合六元环-氮杂卡宾配体(SNHC),并初步证明了该配体比一般的咪唑型五元环氮杂卡宾具有更强的亲核能力和配位能力.在温和条件下, SNHC配体与Ir(Ⅰ)发生快捷的氧化还原配位,生成了含有两个Ir–C共价键的Ir(Ⅲ)钳形有机金属氢化物SNIr-H,产率高达91%.该类配合物在催化C–H活化/C–Si、C–C键形成反应中具有较高的活性和区域选择性,因此有必要合成更多的类似物和衍生物,进一步拓宽并深化该类配合物催化性质研究.本文通过扩展配体类型和Ir–C共价键的杂化模式,进一步转化和衍生该类金属有机配合物.这些化合物为开发新的金属有机试剂、新的催化反应性质提供了物质基础.
In 2014,we designed and synthesized a unique spiro-fused six-membered N-heterocyclic carbene(SNHC),and preliminarily proved that it has stronger nucleophilic nature than the widely reported five-membered carbenes.Taking the advantage of these features of SNHC ligand,we have further succeeded in the convenient synthesis of a series of new and maybe more active Ir(Ⅲ)pincer organometallics 2–5 through conventional transformations.Many complexes derived from complex 1 have high catalytic activity in the C–H activation/C–C bond formation reaction.This paper will introduce the conversion and synthesis of organometallic complexes containing multiple Ir–C covalent bonds.These compounds and their analogues will be helpful to develop new organometallic alkylation reagents or new organometallic catalytic reactions.This case is considerably different from the typical coordination strategies and thus provides an alternative synthetic methodology of organometallics.
作者
言志博
彭猛
谢文平
王鸿
卢卡
彭俊钦
蔡恒
代坤龙
张辅民
张晓明
涂永强
Zhi-Bo Yan;Meng Peng;Wen-Ping Xie;Hong Wang;Ka Lu;Jun-Qin Peng;Heng Cai;Kun-Long Dai;Fu-Min Zhang;Xiao-Ming Zhang;Yong-Qiang Tu(State Key Laboratory of Applied Organic Chemistry&College of Chemistry and Chemical Engineering,Lanzhou University,Lanzhou 730000,China;School of Chemistry and Chemical Engineering,Shanghai Jiao Tong University,Shanghai 200240,China;College of Pharmaceutical Science and Collaborative Innovation Center of Yangtze River Delta Region Green Pharmaceuticals,Zhejiang University of Technology,Hangzhou 310014,China)
出处
《中国科学：化学》
CAS
CSCD
北大核心
2023年第3期516-521,共6页
SCIENTIA SINICA Chimica
基金
中国教育部“111”计划、科技部重大项目(编号:2018ZX09711001-005-002)
上海市科技委员会(编号:19JC1430100)
国家自然科学基金(编号:21502080,21772019,21772076,21871117,91956203,21971095)资助项目。
关键词
螺环稠合氮杂卡宾
衍生合成
金属-碳共价键
迁移插入
spirocyclic NHC framework
derivative synthesis
C–M covalent bonds
migratory insertion
