9 research outputs found
Kinetic Selectivity of Olefin Metathesis Catalysts Bearing Cyclic (Alkyl)(Amino)Carbenes
The evaluation of ruthenium olefin metathesis catalysts 4–6 bearing cyclic (alkyl)(amino)carbenes (CAACs) in the cross-metathesis of cis-1,4-diacetoxy-2-butene (7) with allylbenzene (8) and the ethenolysis of methyl oleate (11) is reported. Relative to most NHC-substituted complexes, CAAC-substituted catalysts exhibit lower E/Z ratios (3:1 at 70% conversion) in the cross-metathesis of 7 and 8. Additionally, complexes 4–6 demonstrate good selectivity for the formation of terminal olefins versus internal olefins in the ethenolysis of 11. Indeed, complex 6 achieved 35 000 TONs, the highest recorded to date. CAAC-substituted complexes exhibit markedly different kinetic selectivity than most NHC-substituted complexes
Latent Ruthenium Olefin Metathesis Catalysts That Contain an N-Heterocyclic Carbene Ligand
A new N-heterocyclic carbene containing olefin metathesis catalyst, (sIMes)(Cl)_2Ru(CH(CH_2)_2-C,N-2-C_5H_4N) (4a), was synthesized from (sIMes)(PCy_3)(Cl)_2RuCHPh (1) or (sIMes)(py)_2(Cl)_2RuCHPh (3). When heated at 40 °C in dichloromethane, 4a is slowly converted to its isomer 4b. The X-ray structures of 4a and 4b show that the NHC and pyridine ligands are trans in 4a and cis in 4b. 4a is more latent than 1 and 4b much more latent than 4a in ring-closing metathesis (RCM) and ring-opening metathesis polymerization (ROMP)
Z-Selective Ethenolysis with a Ruthenium Metathesis Catalyst: Experiment and Theory
The Z-selective ethenolysis activity of chelated ruthenium metathesis catalysts was investigated with experiment and theory. A five-membered chelated catalyst that was successfully employed in Z-selective cross metathesis reactions has now been found to be highly active for Z-selective ethenolysis at low ethylene pressures, while tolerating a wide variety of functional groups. This phenomenon also affects its activity in cross metathesis reactions and prohibits crossover reactions of internal olefins via trisubstituted ruthenacyclobutane intermediates. In contrast, a related catalyst containing a six-membered chelated architecture is not active for ethenolysis and seems to react through different pathways more reminiscent of previous generations of ruthenium catalysts. Computational investigations of the effects of substitution on relevant transition states and ruthenacyclobutane intermediates revealed that the differences of activities are attributed to the steric repulsions of the anionic ligand with the chelating groups
Highly Efficient Ruthenium Catalysts for the Formation of Tetrasubstituted Olefins via Ring-Closing Metathesis
A series of ruthenium-based metathesis catalysts with N-heterocyclic carbene (NHC) ligands have been prepared in which the N-aryl groups have been changed from mesityl to mono-ortho-substituted phenyl (e.g., tolyl). These new catalysts offer an exceptional increase in activity for the formation of tetrasubstituted olefins via ring-closing metathesis (RCM), while maintaining high levels of activity in ring-closing metathesis (RCM) reactions that generate di- and trisubstituted olefins
Latent Ruthenium Olefin Metathesis Catalysts That Contain an N-Heterocyclic Carbene Ligand
<i>Z</i>‑Selective Ethenolysis with a Ruthenium Metathesis Catalyst: Experiment and Theory
The <i>Z</i>-selective ethenolysis activity of chelated
ruthenium metathesis catalysts was investigated with experiment and
theory. A five-membered chelated catalyst that was successfully employed
in <i>Z</i>-selective cross metathesis reactions has now
been found to be highly active for <i>Z</i>-selective ethenolysis
at low ethylene pressures, while tolerating a wide variety of functional
groups. This phenomenon also affects its activity in cross metathesis
reactions and prohibits crossover reactions of internal olefins via
trisubstituted ruthenacyclobutane intermediates. In contrast, a related
catalyst containing a six-membered chelated architecture is not active
for ethenolysis and seems to react through different pathways more
reminiscent of previous generations of ruthenium catalysts. Computational
investigations of the effects of substitution on relevant transition
states and ruthenacyclobutane intermediates revealed that the differences
of activities are attributed to the steric repulsions of the anionic
ligand with the chelating groups
<i>Z</i>‑Selective Ethenolysis with a Ruthenium Metathesis Catalyst: Experiment and Theory
The <i>Z</i>-selective ethenolysis activity of chelated
ruthenium metathesis catalysts was investigated with experiment and
theory. A five-membered chelated catalyst that was successfully employed
in <i>Z</i>-selective cross metathesis reactions has now
been found to be highly active for <i>Z</i>-selective ethenolysis
at low ethylene pressures, while tolerating a wide variety of functional
groups. This phenomenon also affects its activity in cross metathesis
reactions and prohibits crossover reactions of internal olefins via
trisubstituted ruthenacyclobutane intermediates. In contrast, a related
catalyst containing a six-membered chelated architecture is not active
for ethenolysis and seems to react through different pathways more
reminiscent of previous generations of ruthenium catalysts. Computational
investigations of the effects of substitution on relevant transition
states and ruthenacyclobutane intermediates revealed that the differences
of activities are attributed to the steric repulsions of the anionic
ligand with the chelating groups