Anionic N-heterocyclic olefins (aNHOs) are suited well for the stabilization of low-coordinate inorganic complexes, due to their steric tunability and strong σand π-electron donating abilities. In this study, the new two-coordinate zinc complex ( Me IPrCH) 2 Zn ( Me IPrCH = [(MeCNDipp) 2 CCH] − , Dipp = 2,6diisopropylphenyl) is shown to participate in a broad range of metathesis reactions with main group element-based halides and hydrides. In the case of the group 14 halides, Cl 2 E•dioxane (E = Ge and Sn), transmetalation occurs to form dinuclear propellane-shaped cations, [( Me IPrCHE) 2 (μ-Cl)] + , while the aNHO-capped phosphine ligand Me IPrCH-PPh 2 is obtained when ( Me IPrCH) 2 Zn is combined with ClPPh 2 . Lastly, ZnH 2 elimination drives transmetalation between ( Me IPrCH) 2 Zn and hydroboranes and hydroalumanes, leading to Lewis acidic aNHO-supported -boryl and -alane products.