Iodide-sulfides of dysprosium: Elucidation of the pathway to lanthanide iodide-sulfide-nitride clusters

In an attempt to get more insight into the way of formation of recently obtained unusual iodide-sulfidenitride clusters Ln(3)I(5)(S-2)(S2N2)(THF)(10) (Ln = Nd (1), Dy (2)) and modify this synthesis reactions of dysprosium iodide-nitride with sulfur were carried out in various conditions. It was found that the reaction of as prepared dysprosium iodide-nitride [(DyI2)(3)N](x) with sulfur in THF yields ionic complex {[DyI2(THF)(5)](+)[DyI2S5(THF)(2)](-)} (3) anionic part of which contains six-membered cycle DyS5. The same reaction in iso-propylamine medium affords ionic iodide-sulfide{[((PrNH2)-Pr-i)(4)Dy(mu-eta(2):eta(2)-S-2)](2)}(2+)[I-](2)(4) containing bipyramide core formed by two apical Dy3+ cations and two equatorial S2 fragments. The nitride [(DyI)(3)N-2] in THF does not interact with sulfur but upon addition of triiodide DyI3 the reaction affords cluster 2 in moderate yield. (C) 2017 Elsevier B.V. All rights reserved.