On the Reactivity and Stability of Iodide–Nitride–Sulfide Clusters of Neodymium and Dysprosium

Abstract

The thermal decomposition of cluster Nd₃I₅(S₂)(S₂N₂)(THF)10 (I) at 50–400°C affords a mixture of products among which tetrahydrofuran (THF), sulfur, diiodine, HI, H₂S, CS₂, S₃N₆, S₃N₅, MeI, thiophene, tetrahydrothiophene, diiodobutane, iodobutene, and NdI₃ are identified. The treatment of Ln₃I₅(S₂)(S₂N₂)(THF)₁₀ (Ln = Nd (I), Dy (II)) with phenanthroline (Phen) in THF at room temperature results in the partial substitution of ТНF to form new complexes Ln₃I₅(S₂)(S₂N₂)(THF)₄(Phen)₃. The dissolution of compound I in pyridine gives a pyridine (Py) complex Ln₃I₅(S₂)(S₂N₂)(THF)3(Py)₇. The dissolution of compounds I and II in acetonitrile at 20°C is accompanied by the fast rearrangement and fragmentation of the complexes to form LnI₃(MeCN)₆, [LnI(S₂)(MeCN)], and [LnI(S₂N₂)(MeCN)]. Complex I in THF does not react with white phosphorus, carbon monoxide, fullerene C₆₀, and chromium hexacarbonyl.