A novel chelated ruthenium-based metathesis catalyst bearing an N-2,6-diisopropylphenyl group is reported and displays near-perfect selectivity for the Z-olefin (>95%), as well as unparalleled TONs of up to 7,400, in a variety of homodimerization and industrially relevant metathesis reactions. This derivative and other new catalytically-active species were synthesized using an improved method employing sodium carboxylates to induce the salt metathesis and C—H activation of these chelated complexes. All of these new ruthenium-based catalysts are highly Z-selective in the homodimerization of terminal olefins.