Readily Accessible and Easily Modifiable Ru-Based
Catalysts for Efficient and <i>Z</i>‑Selective Ring-Opening
Metathesis Polymerization and Ring-Opening/Cross-Metathesis
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Abstract
Rationally
designed Ru-based catalysts for efficient <i>Z</i>-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 <i>Z</i> selectivity (93:7 to >98:2 <i>Z</i>:<i>E</i>) 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