Extension of Surface Organometallic Chemistry to Metal-Organic Frameworks: Development of a Well-Defined Single Site [(≡Zr-O-)W(âO)(CH2tBu)3] Olefin Metathesis Catalyst.
J Am Chem Soc
; 142(39): 16690-16703, 2020 Sep 30.
Article
em En
| MEDLINE
| ID: mdl-32902976
ABSTRACT
We report here the first step by step anchoring of a W(≡CtBu)(CH2tBu)3 complex on a highly crystalline and mesoporous MOF, namely Zr-NU-1000, using a 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 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 WâO 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 WâO alkyl complexes from their W carbyne analogues.
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01-internacional
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MEDLINE
Idioma:
En
Ano de publicação:
2020
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Article