The synthesis, characterization, and catalytic activity of nonclassical iron(II) polyhydride complexes containing tridentate PNP pincer-type ligands is described. These compounds of the general formula [Fe(PNP)(H)2(η2-H2)] exhibit remarkable reactivity toward terminal alkynes. They efficiently promote the catalytic dimerization of aryl acetylenes giving the corresponding conjugated 1,3-enynes in excellent yields with low catalyst loadings. When the reaction is carried out in the presence of pinacolborane, vinyl boronates are obtained. Both reactions take place under mild conditions and are highly chemo-, regio-, and stereoselective with up to 99% Z-selectivity.