南方科技大学知识苑(SUSTech KC): Cobalt(-I)- and Rhodium(-I)-Mediated Dearylation of N-Aryl N-Heterocyclic Carbene Ligands

题名	Cobalt(-I)- and Rhodium(-I)-Mediated Dearylation of N-Aryl N-Heterocyclic Carbene Ligands
作者	Wang, Peng 1; Cheng, Jun 1; Wang, Dongyang2 ; Yang, Chengbo 1; Leng, Xuebing 1; Deng, Liang 1,2
通讯作者	Deng, Liang
发表日期	2020-08-10
DOI	10.1021/acs.organomet.0c00383
发表期刊	ORGANOMETALLICS 影响因子和分区
ISSN	0276-7333
EISSN	1520-6041
卷号	39 期号:15页码:2871-2877
摘要	N-heterocyclic carbene (NHC) ligands are intensively used in transition-metal-catalyzed reactions. Their bond-activation reactions, however, are much less understood. We now report unprecedented dearylation reactions of N-aryl-substituted NHCs mediated by cobalt(-I) and rhodium(-I) species, which lead to the conversion of N-aryl NHCs into N-aryl imidazolate ligands. The reduction reactions of [(IMes)Co(eta(2):eta(2)-dvtms)] (IMes = 1,3-dimesitylimidazol-2-ylidene, dvtms = divinyltetramethyldisiloxane) and [Rh(cod)Cl](2)/IPr (cod = cycloocta-1,5-diene, IPr = 1,3-bis(2',6'-diisopropylphenyl)imidazol-2-ylidene) with KC8 and 18-crown-6 gave the corresponding N-aryl imidazolate complexes [(18-crown-6)K(mu-C(3)H(2)N(2)Mes-kappa C-2,kappa N-3)Co(eta(2):eta(2)-dvtms)] (1) and [K(18-crown-6) (THF)] [(eta(2):eta(2)-cod)(2)Rh-2(mu-C3H2N2(Dipp)-kappa C-2,kappa N-3)(2)(mu-Dipp)(2)K] (3), which have been characterized by NMR and X-ray diffraction studies. In supporting the possible involvement of cobalt(-I) and rhodium(-I) species in the dearylation reactions, the three-coordinate formal cobalt(-I) and rhodium(-I) complexes [K(2,2,2-Crypt)] [(ICy)Co(eta(2):eta(2)-dvtms)] (2) and [K(18-crown-6)][(IPr)Rh(eta(2):eta(2) dvtms)] (5) have been obtained from the reduction reactions of [(ICy)Co(eta(2):eta(2)-dvtms)] (ICy = 1,3-dicyclohexylimidazol-2-ylidene) and [Rh(dvtms)Cl](2)/IPr with KC8 and crown ethers. These results suggest that the C-N bond cleavage step of the dearylation reactions is likely achieved by cobalt(-I)-/rhodium(-I)-mediated C-N bond oxidative addition and also imply the possible involvement of similar degradation reactions in N-aryl NHC-transition-metal-catalyzed reactions operating under strong reducing conditions.
相关链接	[来源记录]
收录类别	SCI ; EI
语种	英语
学校署名	通讯
资助项目	National Natural Science Foundation of China[21725104][21690062][21821002] ; National Key Research and Development Program[2016YFA0202900] ; Strategic Priority Research Program of the Chinese Academy of Sciences[XDB20000000] ; Program of Shanghai Academic Research Leader[19XD1424800]
WOS研究方向	Chemistry
WOS类目	Chemistry, Inorganic & Nuclear ; Chemistry, Organic
WOS记录号	WOS:000562124400009
出版者	AMER CHEMICAL SOC
EI入藏号	20203309033878
EI主题词	Rhodium compounds ; Cobalt compounds ; Organic compounds ; Transition metals
EI分类号	Metallurgy and Metallography:531 ; Physical Chemistry:801.4 ; Organic Compounds:804.1
ESI学科分类	CHEMISTRY
来源库	Web of Science
引用统计	被引频次[WOS]：11
成果类型	期刊论文
条目标识符	http://sustech.caswiz.com/handle/2SGJ60CL/186753
专题	深圳格拉布斯研究院
作者单位	1.Univ Chinese Acad Sci, Chinese Acad Sci, Ctr Excellence Mol Synth,Shanghai Inst Organ Chem, State Key Lab Organometall Chem,Shanghai Hong Kon, Shanghai 200032, Peoples R China 2.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Shenzhen 518055, Peoples R China
通讯作者单位	深圳格拉布斯研究院
推荐引用方式 GB/T 7714	Wang, Peng,Cheng, Jun,Wang, Dongyang,et al. Cobalt(-I)- and Rhodium(-I)-Mediated Dearylation of N-Aryl N-Heterocyclic Carbene Ligands[J]. ORGANOMETALLICS,2020,39(15):2871-2877.
APA	Wang, Peng,Cheng, Jun,Wang, Dongyang,Yang, Chengbo,Leng, Xuebing,&Deng, Liang.(2020).Cobalt(-I)- and Rhodium(-I)-Mediated Dearylation of N-Aryl N-Heterocyclic Carbene Ligands.ORGANOMETALLICS,39(15),2871-2877.
MLA	Wang, Peng,et al."Cobalt(-I)- and Rhodium(-I)-Mediated Dearylation of N-Aryl N-Heterocyclic Carbene Ligands".ORGANOMETALLICS 39.15(2020):2871-2877.