Qureshi Ziyauddin S, Hamieh Ali, Barman Samir, Maity Niladri, Samantaray Manoja K, Ould-Chikh Samy, Abou-Hamad Edy, Falivene Laura, D'Elia Valerio, Rothenberger Alexander, Llorens Isabelle, Hazemann Jean-Louis, Basset Jean-Marie
KAUST Catalysis Center (KCC), King Abdullah University of Science and Technology (KAUST) , 23955-6900 Thuwal, Saudi Arabia.
Department of Materials Science and Engineering, School of Molecular Science and Engineering, Vidyasirimedhi Institute of Science and Technology (VISTEC) , 21210, Wang Chan, Rayong, Thailand.
Inorg Chem. 2017 Jan 17;56(2):861-871. doi: 10.1021/acs.inorgchem.6b02424. Epub 2017 Jan 5.
Synthesis, structure, and olefin metathesis activity of a surface complex [(≡Si-O-)W(═O)(CH)-ImN] (4) (Im = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato) supported on silica by a surface organometallic chemistry (SOMC) approach are reported. The reaction of N-silylated 2-iminoimidazoline with tungsten(VI) oxytetrachloride generated the tungsten oxo imidazolin-2-iminato chloride complex [ImNW(═O)Cl] (2). This was grafted on partially dehydroxylated silica pretreated at 700 °C (SiO) to afford a well-defined monopodal surface complex [(≡Si-O-)W(═O)Cl-ImN] (3). 3 underwent alkylation by ZnMe to produce [(≡Si-O-)W(═O)(CH)-ImN] (4). The alkylated surface complex was thoroughly characterized by solid-state NMR, elemental microanalysis, Raman, FT-IR spectroscopies, and XAS analysis. 4 proved to be an active precatalyst for self-metathesis of terminal olefins such as propylene and 1-hexene.
报道了通过表面有机金属化学（SOMC）方法负载在二氧化硅上的表面配合物[(≡Si-O-)W(═O)(CH)-ImN] (4)（Im = 1,3-双(2,6-二异丙基苯基)咪唑啉-2-亚氨基）的合成、结构和烯烃复分解活性。N-硅烷基化的2-亚氨基咪唑啉与四氯氧化钨(VI)反应生成氧代咪唑啉-2-亚氨基氯化钨配合物[ImNW(═O)Cl] (2)。将其接枝到在700 °C预处理的部分脱羟基二氧化硅(SiO)上，得到明确的单足表面配合物[(≡Si-O-)W(═O)Cl-ImN] (3)。3通过ZnMe进行烷基化反应生成[(≡Si-O-)W(═O)(CH)-ImN] (4)。通过固态NMR、元素微量分析、拉曼光谱、FT-IR光谱和XAS分析对烷基化表面配合物进行了全面表征。4被证明是用于末端烯烃如丙烯和1-己烯自复分解的活性预催化剂。
