Shi Xianghui, Qin Guorui, Wang Yang, Zhao Lanxiao, Liu Zhizhou, Cheng Jianhua
State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, No. 5625, Renmin Street, Changchun, 130022, China.
University of Chinese Academy of Sciences, Changchun Branch, Changchun, 130022, China.
Angew Chem Int Ed Engl. 2019 Mar 22;58(13):4356-4360. doi: 10.1002/anie.201814733. Epub 2019 Feb 19.
Hydrogenolysis of the half-sandwich penta-arylcyclopentadienyl-supported heavy alkaline-earth-metal alkyl complexes (Cp )AeCH(SiMe ) (Cp =C Ar , Ar=3,5- Pr -C H S=THF or DABCO) in hexane afforded the calcium, strontium, and barium metal-hydride complexes as the same dimers [(Cp )Ae(μ-H)(S)] (Ae=Ca, S=THF, 2-Ca; Ae=Sr, Ba, S=DABCO, 4-Ae), which were characterized by NMR spectroscopy and single-crystal X-ray analysis. 2-Ca, 4-Sr, and 4-Ba catalyzed alkene hydrogenation under mild conditions (30 °C, 6 atm, 5 mol % cat.), with the activity increasing with the metal size. A variety of activated alkenes including tri- and tetra-substituted olefins, semi-activated alkene (Me SiCH=CH ), and unactivated terminal alkene (1-hexene) were evaluated.
在己烷中，对半夹心五芳基环戊二烯基负载的重碱土金属烷基配合物（Cp）AeCH(SiMe₃)₂（Cp = C₅Ar₅，Ar = 3,5 - Prⁱ - C₆H₃，S = THF或DABCO）进行氢解反应，得到钙、锶和钡的金属氢化物配合物，它们为相同的二聚体[(Cp)Ae(μ - H)(S)]（Ae = Ca，S = THF，2 - Ca；Ae = Sr，Ba，S = DABCO，4 - Ae），通过核磁共振光谱和单晶X射线分析对其进行了表征。2 - Ca、4 - Sr和4 - Ba在温和条件下（30 °C，6 atm，5 mol %催化剂）催化烯烃氢化反应，活性随金属原子尺寸增大而增加。对包括三取代和四取代烯烃、半活化烯烃（Me₃SiCH = CH₂）和未活化末端烯烃（1 - 己烯）在内的多种活化烯烃进行了评估。
