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Probing Stereoselectivity in Ring-Opening Metathesis Polymerization Mediated by Cyclometalated Ruthenium-Based Catalysts: A Combined Experimental and Computational Study
journal contribution
posted on 2016-02-10, 17:50 authored by L. E. Rosebrugh, T. S. Ahmed, V. M. Marx, J. Hartung, P. Liu, J. G. López, K. N. Houk, R. H. GrubbsThe microstructures of polymers produced
by ring-opening metathesis
polymerization (ROMP) with cyclometalated Ru-carbene metathesis catalysts
were investigated. A strong bias for a cis,syndiotactic microstructure with minimal head-to-tail bias
was observed. In instances where trans errors were
introduced, it was determined that these regions were also syndiotactic.
Furthermore, hypothetical reaction intermediates and transition structures
were analyzed computationally. Combined experimental and computational
data support a reaction mechanism in which cis,syndio-selectivity is a result of stereogenic metal control,
while microstructural errors are predominantly due to alkylidene isomerization
via rotation about the RuC double bond.
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polymerciRumetathesiPolymerizationMediatedsyndiotacticCyclometalatedcomputationallyROMPalkylidene isomerizationpolymerizationinstanceCatalystStereoselectivitycyclometalatedstereogenic metal controlreaction intermediatescatalysttrans errorsdata supportrotationExperimentalregionreaction mechanismMetathesiComputational StudyThe microstructuresbiasmicrostructural errorsbondtransition structures
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