Access to the first (iminophosphoranyl)(selenophosphoranyl)methane ligands Ph<sub>2</sub>P(Se)CH<sub>2</sub>P(NR)Ph<sub>2</sub>: coordination of their methanide and methandiide anions to ruthenium
elemental selenium. In the presence of Et3N, these ligands react with [RuCl(μ-Cl)(η6-p-cymene)}2] to afford mononuclear Ru(II) species in which the resulting methanide anions adopt a tridentate coordination. Further deprotonation with KH generates carbenic ruthenium derivatives which participate, under remarkably mildconditions, in C–C coupling processes with isocyanides.