- Extension of surface organometallic chemistry to metal?organic frameworks: Development of a well-defined single site [(≡Zr? O?)W(=O)(CH2TBu)3] olefin metathesis catalyst
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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 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.
- Thiam, Zeynabou,Abou-Hamad, Edy,Dereli, Busra,Liu, Lingmei,Emwas, Abdul-Hamid,Ahmad, Rafia,Jiang, Hao,Isah, Abdulrahman Adamu,Ndiaye, Papa Birame,Taoufik, Mostafa,Han, Yu,Cavallo, Luigi,Basset, Jean-Marie,Eddaoudi, Mohamed
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supporting information
p. 16690 - 16703
(2020/11/09)
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- Tergal Gland Secretion of the Rove Beetle Aleochara pseudochrysorrhoa (Staphylinidae: Aleocharinae): Chemical Composition and Biological Roles
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Aleochara pseudochrysorrhoa has a glandular complex known as the tergal gland. Generally, the tergal gland secretion (TGS) has been described to have defensive function, but some reports point to a possible secondary function of this complex. For example, the TGS of the related species A. curtula has been demonstrated to possess an important role in intraspecies communication. In this work, we describe the chemical composition of the TGS of A. pseudochrysorrhoa males and females. Eleven compounds were identified based on GC/MS and GC-FT-IR analyses, retention indexes and derivatization products. Furthermore, a brief study regarding the biological function of the TGS in mating behavior is provided, in which the stimulation of male grasping response reaction by female TGS proved to be dependent on concentration.
- da Silva, Maycon R.,Vidal, Diogo M.,Figueiredo, Leonardo,Bandeira, Pamela T.,Bergmann, Jan,Zarbin, Paulo H. G.
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- Manganese-catalyzed cross-coupling reaction between aryl grignard reagents and alkenyl halides
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(Chemical Equation Presented) Aryl Grignard reagents react stereospecifically with alkenyl halides in the presence of manganese chloride (10%) to afford good yields of cross-coupling products.
- Cahiez, Gerard,Gager, Olivier,Lecomte, Fabien
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supporting information; experimental part
p. 5255 - 5256
(2009/05/30)
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- PHASE-TRANSFER VERSION OF THE WITTIG REACTION AND ITS STEREOCHEMISTRY IN THE ALIPHATIC SERIES
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Alkyltriphenylphosphonium salts react with saturated α,β-ethylenic, α,β-acetylenic, and cyclic aliphatic aldehydes when heated with solid potassium carbonate to form the corresponding alkenes with preparative yields.The reaction is cis-stereoselective with saturated aldehydes and cis-stereospecific with unsaturated aldehydes.
- Khusid, A. Kh.,Kovalev, B. G.
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- A NOVEL ZIRCONIUM-CATALYZED HYDROALUMINATION OF OLEFINS
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Sterically hindered trialkylalanes, such as triisobutylalane, react with olefins at or below room temperature under the influence of a catalytic amount of Cl2ZrCp2 to effect hydroalumination of the olefins.The reaction can tolerate certain hetero-functional groups, such as OH, SPh and Br, which tend to interfere with previously reported hydroalumination procedures.
- Negishi, Ei-ichi,Yoshida, Tadao
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p. 1501 - 1504
(2007/10/02)
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