The reactions of europium and yttrium with N-iodine-triphenylphosphoraneimine. Crystal structures of [EuI2(DME)(3)], [Eu2I(NPPh3)(5)(DME)] and [Y2I(NPPh3)(4)(THF)(4)]I-+(3)-

When treated with ultrasound, the reaction of europium metal with INPPh3 in 1,2-dimethoxyethane (DME) leads to the complexes [EuI2(DME)(3)] (1) and [E u2I(NPPh3)(5)(DME)] (2) which are separated from each other by fractional c rystallization. On the other hand, the reaction of yttrium metal with INPPh 3 under similar conditions in THF gives the ionic phosphoraneiminato comple x [Y2I(NPPh3)(4)(THF)(4)]I-+(3)- (3). All complexes are characterized by cr ystal structure determinations. 1: Space group P2(1), Z = 2, lattice dimensions at 188 K: a = 848.9(1); b = 1059.4(1); c = 1227.9(1) pm; beta = 93.793(6)degrees; R = 0.0246. In the m olecular structure of 1 the europium atom is eightfold coordinated with a b ond angle I-Eu-I of 158.51 degrees. 2 . 2DME: Space group P (1) over bar, Z = 2, lattice dimensions at 193 K: a = 1405.5(1); b = 1652.2(2); c = 2203.7(2) pm; alpha = 89.404(11)degrees; b eta = 72.958(11)degrees; gamma = 78.657(11)degrees; R = 0.0391. In 2 the eu ropium atoms are linked by the mu-N-atoms of two (NPPh3-) groups to form a planar Eu2N2 four-membered ring. One of the Eu atoms is terminally coordina ted by the N atoms of two (NPPh3-) groups, thus achieving a distorted tetra hedral surrounding. The second Eu atom is coordinated by the N atom of one (NPPh3-) group, by the terminally bounded iodine atom and by the oxygen ato ms of the DME chelate, thus achieving a distorted octahedral surrounding. 3 . 61/2THF: Space group P1, Z = 2, lattice dimensions at 103 K: a = 1739.7 (2); b = 1770.1(2); c = 2153.8(3) pm; alpha = 74.929(15)degrees; beta = 84. 223(14)degrees; gamma = 64(.)612(12)degrees; R = 0.0638. In the cation [Y2I (NPPh3)(4)(THF)(4)](+) of 3 the yttrium atoms are linked by the mu-N atoms of two (NPPh3-) groups as well as by the mu-I atom. One (NPPh3-) ligand and two THF molecules complete the distorted octahedral coordination at each y ttrium atom.