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Increasing Olefin Metathesis Activity of Silica‐Supported Molybdenum Imido Adamantylidene Complexes through E Ligand σ‐Donation
- Source :
- Helvetica Chimica Acta, 104 (11)
- Publication Year :
- 2021
- Publisher :
- Wiley, 2021.
-
Abstract
- Molybdenum imido adamantylidene complexes with different substituents on the imido ligand (dipp=2,6-diisopropylphenyl, Ar-F5=C6F5, and Bu-t) having distinct electron donating abilities were investigated for the metathesis of internal and terminal olefins, for both molecular and silica-supported species using standardized protocols. Here we show that surface immobilization of these compounds results in dramatically increased activity compared to their molecular counterparts. Additionally, we show that electron withdrawing imido groups increase the activity of the compound towards terminal olefins while they simultaneously decrease the ability to metathesize internal olefins. Furthermore, these systems also show high stability when used as initiators in olefin metathesis, although the species that display higher initial activity deactivate faster than those that show more a more moderate reaction rate at first. Our catalytic studies, augmented by DFT calculations, show that all investigated compounds have a remarkably small energy difference between the trigonal bipyramidal (TBP) and square planar (SP) configurations of the metallacyclobutane intermediates, which has previously been linked to high activity.<br />Helvetica Chimica Acta, 104 (11)<br />ISSN:0018-019X<br />ISSN:1522-2675
- Subjects :
- Olefin metathesis
Ligand
Organic Chemistry
chemistry.chemical_element
surface chemistry
Biochemistry
Medicinal chemistry
Catalysis
adamantylidenes
Inorganic Chemistry
molybdenum
chemistry
Molybdenum
electron donation
olefin metathesis
surface organometallic chemistry
Drug Discovery
Physical and Theoretical Chemistry
Subjects
Details
- ISSN :
- 15222675 and 0018019X
- Volume :
- 104
- Database :
- OpenAIRE
- Journal :
- Helvetica Chimica Acta
- Accession number :
- edsair.doi.dedup.....649231069946f16bbc19f851a326049e