Reactivity of (THF)4Ca(PPh2)2 in stoichiometric and catalytic reactions (thf)4Ca(PPh2)2 with very good yields and under mild conditions. Beside the enormous reactivity of (thf)4Ca(PPh2)2 regarding hydrophosphanylation reactions the diphenylphosphanide ligand is also able to act as Lewis base. In fact reactions of (thf)4Ca(PPh2)2 with iron carbonyl complexes afforded [(thf)4Ca{Fe2(CO)6(Mikro CO)(Mikro PPh2)}2]. Reaction with elemental chalcogenides led to the formation of the respective diphenylphosphinates (thf)3Ca(S2PPh2)2 (thf)3Sr(S2PPh2)2 (thf)2Ca(Se2PPh2)2 and (thf)3Sr(Se2PPh2)2. All of these compounds are colorless crystalline solids which are stable under atmospheric conditions.