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：Liu, Guifeng;刘贵锋

通信作者：Yan, H[1]

机构：[1]Nanjing Univ, Sch Chem & Chem Engn, State Key Lab Coordinat Chem, Nanjing 210093, Jiangsu, Peoples R China;[2]Chinese Acad Forestry, Inst Chem Ind Forest Prod, Nanjing 210042, Jiangsu, Peoples R China

年份：2015

卷号：34

期号：3

起止页码：591-598

外文期刊名：ORGANOMETALLICS

收录：;WOS:【SCI-EXPANDED(收录号:WOS:000349273900009)】；

基金：This work was supported by the National Natural Science Foundation of China (21271102), the National Basic Research Program of China (2013CB922101), the Natural Science Foundation of Jiangsu Province (BK20130054), and the High Performance Computing Center of Nanjing University.

语种：英文

外文关键词：Carbon - Hydrocarbons - Metals - Molecules - Silica - Sulfur compounds - Temperature

摘要：The three-component reactions of the 16-electron half sandwich complex CpCo(S2C2B10H10) (Cp = cyclopentadienyl) (1) with ethyl diazoacetae (EDA) and alkynes R-1 R-2 (R-1 = Ph, R-2 = H; R-1 = CO2Me, R-2 = H; R-1 = R-2 = CO2Me; R-1 = Fc, R-2 = H) at ambient temperature lead to compounds CpCo(S2C2B10H9) (CH2CO2Et) (CHCO2Et) (R-1=R-2) (2-5), CpCo(S2C2B10H9)(CH2CO2Et)(R-1=R-2) (2-5), CpCo(S2C2B10H9)(CH2CO2Et)(R-2-R-1-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 ethnylferrocene 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)(R-1=R-2) (12-14) accompanied by the coordination of the tow 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.