厦门大学学报（自然科学版）2018，Vol.57Issue(1)：9-17,9.DOI:10.6043/j.issn.0438-0479.201703044
氮杂环卡宾在三吡唑基硼酸阴离子为支撑配体的钌中心上的环金属化
Cyclometalation of N-Heterocyclic Carbene on Ruthenium Center Supported by Tris(pyrazolyl)borate Anion
摘要
Abstract
Inspired by the rich reactivity and catalytic properties of the tris(pyrazolyl)borate anion (Tp)ruthenium complex TpRuCl (PPh3 )2 and the advantage of N-heterocyclic carbene (NHC)over the traditional phosphine ligand,the reaction of TpRuCl(PPh3 )2 with the NHC ligand 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene (H2IMes)was investigated to obtain the TpRu (NHC)complex analogous to the versatile precursor TpRuCl(PPh3 )2 .The reaction proceeded to give the NHC-cyclometalated pro-duct,TpRu(H2IMes-H)(PPh3 )(H2IMes-H=the deprotonated form of H2IMes)instead of the expected TpRuCl(H2IMes) (PPh3 ),in which the C—H bond activation of the o-methyl on the N-bound wingtip of the H2IMes ligand occurred.Heating a solu-tion of the isolated compound TpRu(H2IMes-H)(PPh3 )in CH2Cl2 led to the dissociation of the PPh3 ligand and further activation of the metalated benzyl C—H on the ruthenium center via α-H elimination,which was then followed by a hydride/chloride metathesis between the Ru—H intermediate and CH2Cl2 solvent to result in the bis-carbene chelated compound TpRuCl(H2IMes-2 H).关键词
三吡唑基硼酸阴离子/氮杂环卡宾/卡宾/钌/环金属化Key words
tris(pyrazolyl)borate anion/N-heterocyclic carbene/carbene/ruthenium/cyclometalation分类
化学化工引用本文复制引用
于谦,林毅,聂鹏,温庭斌..氮杂环卡宾在三吡唑基硼酸阴离子为支撑配体的钌中心上的环金属化[J].厦门大学学报（自然科学版）,2018,57(1):9-17,9.基金项目
国家重点基础研究发展计划(973 计划)(2012CB821600) （973 计划）
