文献类型：期刊文献

英文题名：Metal-induced B-H activation in three-component reactions: 16-electron complex CpCo(S2C2B10H10), ethyl diazoacetate, and alkynes

作者：Liu, Guifeng[1,2] Yan, Hong[1]

第一作者：刘贵锋;Liu, Guifeng

通信作者：Yan, Hong

机构：[1] State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, Jiangsu, 210093, China; [2] Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, Nanjing, Jiangsu, 210042, China

年份：2015

卷号：34

期号：3

起止页码：591-598

外文期刊名：Organometallics

收录：EI(收录号：20150700525458);Scopus(收录号：2-s2.0-84922637600)

语种：英文

外文关键词：Temperature - Metals - Molecules - Silica - Activation analysis - Hydrocarbons - Lead compounds - Carbon

摘要：The three-component reactions of the 16-electron half-sandwich complex CpCo(S2C2B10H10) (Cp = cyclopentadienyl) (1) with ethyl diazoacetate (EDA) and alkynes R1≡R2 (R1 = Ph, R2 = H; R1 = CO2Me, R2 = H; R1 = R2 = CO2Me; R1 = Fc, R2 = H) at ambient temperature lead to compounds CpCo(S2C2B10H9)(CH2CO2Et) (CHCO2Et)(R1=R2) (2-5), CpCo(S2C2B10H9)(CH2CO2Et)(R2-R1-CHCO2Et) (6-9), CpCo(S2C2B10H9)(CH2CO2Et)(CH(Ph)C=CHCO2Et) (10), and CpCo(S2C2B10H9)(CH2CO2Et)(CH(Fc)-CH-CCO2Et) (11). In 2-5, one alkyne is stereoselectively inserted into the Co-B bond, one EDA molecule is used to form a sulfide ylide, and the second EDA molecule is inserted into one Co-S bond to form a three-membered metallacyclic ring. At ambient temperature 2-5 undergo rearrangement to 6-9 through migratory insertion of the inserted EDA. Different from 2-5, in 10 phenylacetylene is inserted into the Co-B bond at the terminal carbon and the terminal carbon is coupled with one EDA to afford a six-membered metallacyclic ring with the C=O coordination to metal. In 11, a stable Co-B bond is generated, and one EDA and one ethynylferrocene are inserted into the Co-S bond. Moreover, if weakly basic silica is present, 2-4 can lose an apex BH close to the two carbon atoms of o-carborane to give rise to CpCo(S2C2B9H9)(CH2CO2Et)2(R1=R2) (12-14) accompanied by the coordination of the two sulfide ylide units to the metal center. The solid-state structures of 2-4, 6-12, and 14 were characterized by X-ray structural analysis. ? 2015 American Chemical Society.