Unraveling the Mechanism of 1,3-Diyne Cross-Metathesis Catalyzed by Silanolate-Supported Tungsten Alkylidyne Complexes
نویسندگان
چکیده
منابع مشابه
Alkyne metathesis by molybdenum and tungsten alkylidyne complexes.
Alkyne metathesis by molybdenum and tungsten alkylidyne complexes is now ~45 years old. Progress in the practical aspects of alkyne metathesis reactions with well-defined complexes, as well as applications, in the last decade, guarantees that it is destined to become a useful method for the synthesis of organic molecules.
متن کاملRecent advances in the development of alkyne metathesis catalysts
The number of well-defined molybdenum and tungsten alkylidyne complexes that are able to catalyze alkyne metathesis reactions efficiently has been significantly expanded in recent years.The latest developments in this field featuring highly active imidazolin-2-iminato- and silanolate-alkylidyne complexes are outlined in this review.
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The mechanism of enyne metathesis catalyzed by first and second generation Grubbs complexes has been computationally explored at the DFT level. The relative reactivity and the regioselectivity for the reaction of differently substituted alkenes and alkynes with model Ru complexes has been studied. The usually accepted dissociative mechanism for the alkene metathesis has been explored for alkyne...
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The first highly Z- and enantioselective class of ring-opening/cross-metathesis reactions is presented. Transformations are promoted in the presence of <2 mol % of chiral stereogenic-at-Mo monoaryloxide complexes bearing an adamantylimido ligand that are prepared and used in situ. Reactions involve meso oxabicyclic substrates and afford the desired pyrans in 50-85% yield and up to >98:<2 enanti...
متن کاملThermodynamic and Structural Factors That In fl uence the Redox 2 Potentials of Tungsten − Alkylidyne Complexes
8 ABSTRACT: The thermodynamic and structural factors that influence the redox properties of 9 an extensive set of tungsten−alkylidyne complexes W(CR)L4X are analyzed by combining 10 synthesis, electrochemistry, and computational modeling based on free energy calculations of 11 oxidation potentials at the density functional theory level. The observed linear correlations 12 among oxidation potent...
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ژورنال
عنوان ژورنال: Chemistry - A European Journal
سال: 2018
ISSN: 0947-6539
DOI: 10.1002/chem.201802561