ja404208a_si_001.cif (27.73 kB)
Readily Accessible and Easily Modifiable Ru-Based Catalysts for Efficient and Z‑Selective Ring-Opening Metathesis Polymerization and Ring-Opening/Cross-Metathesis
datasetposted on 2016-02-19, 03:26 authored by R. Kashif M. Khan, Sebastian Torker, Amir H. Hoveyda
Rationally designed Ru-based catalysts for efficient Z-selective olefin metathesis are featured. The new complexes contain a dithiolate ligand and can be accessed in a single step from commercially available precursors in 68–82% yield. High efficiency and exceptional Z selectivity (93:7 to >98:2 Z:E) were achieved in ring-opening metathesis polymerization (ROMP) and ring-opening/cross-metathesis (ROCM) processes; the transformations typically proceed at 22 °C and are operationally simple to perform. Complete conversion was observed with catalyst loadings as low as 0.002 mol %, and turnover numbers of up to 43 000 were achieved without rigorous substrate purification or deoxygenation protocols. X-ray data and density functional theory computations provide support for key design features and shed light on mechanistic attributes.
EfficientattributemetathesiPolymerizationselectivitydeoxygenation protocolsHigh efficiencycatalyst loadingspolymerizationROCMcomplexCatalystolefindesign featurestransformationdithiolate ligandturnover numbersmoldata43 000Accessiblesubstrate purificationROMPprecursordensityModifiableMetathesi0.002Complete conversiontheory computations