Milder routes to chelated ruthenium complexes for Z-selective metathesis
2013
A novel method to effect the salt metathesis and C-H activation of ruthenium-based, Z-selective metathesis catalysts contg. a
chelated N-heterocyclic carbene (NHC) ligand using sodium carboxylates is reported. This method allows for the successful
formation of stable chelated species contg. a variety of alterations to the NHC ligand that had decompd. under the previous
approach. As such, several new, chelated metathesis-active ruthenium complexes are described, including a catalyst system
exhibiting >95% Z-selectivity and record TONs (up to 8100) in homodimerization reactions of terminal olefins. Moreover, a
catalyst has been synthesized that gives highly cis, highly tactic polymers via ring opening metathesis polymn. of strained, cyclic
olefins, marking the first time tactic polymers have been made using a ruthenium-based metathesis catalysts.
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