Extension of the Surface Organometallic Chemistry to Metal-Organic Framework: development of well-defined single site [(≡Zr-O-)W(=O)(CH2tBu)3] olefin metathesis catalyst.
Embargo End Date2021-09-09
Emwas, Abdul-Hamid M.
Isah, Abdulrahman Adamu
Ndiaye, Papa Birame
KAUST DepartmentAdvanced Membranes and Porous Materials Research Center
Chemical Science Program
Functional Materials Design, Discovery and Development (FMD3)
Imaging and Characterization Core Lab
KAUST Catalysis Center (KCC)
Nanostructured Functional Materials (NFM) laboratory
Physical Science and Engineering (PSE) Division
Online Publication Date2020-09-09
Print Publication Date2020-09-30
AbstractWe report here the first step by step anchoring of a W(≡CtBu)(CH2 tBu)3 complex on a highly crystalline and mesoporous MOF, namely Zr-NU-1000, using Surface organometallic Chemistry (SOMC) concept and methodology. SOMC allowed us to selectively graft the complex on the Zr6 clusters and characterize the obtained single site material by using state of the art experimental methods including extensive solid-state NMR techniques and HAADF-STEM imaging. Further FT-IR spectroscopy revealed the presence of a W=O moiety arising from the in situ reaction of the W≡CtBu functionality with the coordinated water coming from the 8-connected hexanuclear Zr6 clusters. All the steps leading to the final grafted molecular complex have been identified by DFT. The obtained material was tested for gas phase and liquid phase olefin metathesis and exhibited higher catalytic activity than the corresponding catalysts synthesized by different grafting methods. This contribution establishes the importance of applying SOMC to MOF chemistry to get well defined single site catalyst on MOF inorganic secondary building units, in particular the in situ synthesis of W=O alkyl complexes from their W carbyne analogues.
CitationThiam, Z., Abou-Hamad, E., Dereli, B., Liu, L., Emwas, A.-H., Ahmad, R., … Eddaoudi, M. (2020). Extension of the Surface Organometallic Chemistry to Metal-Organic Framework: development of well-defined single site [(≡Zr-O-)W(=O)(CH2tBu)3] olefin metathesis catalyst. Journal of the American Chemical Society. doi:10.1021/jacs.0c06925
AcknowledgementsDr. Karim Adil, Dr. Anissa Bendjeriou and Dr. Youssef Belmabkhout are thanked for fruitful discussions.
The authors gratefully acknowledge financial support from King Abdullah University of Science and Technology (KAUST), Kingdom of Saudi Arabia.