Phosphoraneiminato complexes of bismuth(III). Crystal structures of [BiF2(NPEt3) (HNPEt3)](2) and [Bi2I(NPPh3)4]I-3

[BiF2(NPEt3)(HNPEt3)](2) (1) has been obtained by the reaction of BiF3 with Me3SiNPEt3 at 100 degrees C and subsequent extraction with 1,2-dimethoxyet hane in the presence of traces of water forming pale-yellow, moisture sensi tive crystals, which were characterized by a crystal structure determinatio n. Space group P2(1)/n, Z = 4, lattice dimensions at -83 degrees C: a = 210 5.0, b = 1195.8, c = 728.2 pm, beta = 92.55 degrees. 1 forms centrosymmetri c dimeric molecules, in which the Bi atoms are linked via Bi-N bonds of var ying length (213.9 and 240.1 pm) of the NPEt3- groups to form a Bi2N2 four- membered ring. The longer one of the two Bi-N bonds is trans to one termina l F atom. [Bi2I(NPPh3)(4)]I-3 (2) has been obtained by the reaction of bismuth with N -iodine triphenylphosphaneimine in dichloromethane forming red crystals. Cr ystal structure determination of 2 . 2.5 CH2Cl2: Space group P2(1)/n, Z = 4 , lattice dimensions at -50 degrees C: a = 1542.6, b = 2409.1, c = 2173.5 p m, beta = 105.82 degrees. In 2 the Bi atoms are linked via two N atoms of t wo NPPh3- groups to form a non-planar Bi2N2 four-membered ring with a fold angle of 27 degrees along the N ... N connection line. The two remaining NP Ph3- groups are terminally connected and bent in the same direction. The io dide ion caps the two Bi atoms so that a [Bi2I(NPPh3)(4)](+) cation is form ed.