Two new [12]metallacrown-6 compounds, [M-6(II)(SMe)(12)] [M = Ru (1), Zn (2)], were constructed from a dimethyl sulfoxide decomposed methylthiol product to doubly bridged metal centers. The Ru-II compound can prompt alkenylation reactions of phenylpyridines with alkynes to generate monoalkenylated arylpyridines in moderate yields with high regioselectivity and stereoselectivity.