Synthesis and crystal structures of the phosphoraneiminato complexes [SnI(NPPh3)](2) and [SnI3(NPPh3)](2)

The phosphoraneiminato complex of the divalent tin, [SnI(NPPh3)](2) (1), or iginates from the reaction of metallic tin with N-iodine triphenylphospbane imine, INPPh3, in dichloromethane suspension. 1 forms yellow, moisture sens itive crystals, which can be converted into the red phosphoraneiminato comp lex of the tetravalent tin, [SnI3(NPPh3)](2) (2), by oxidation with iodine. According La the crystal structure analyses 1 and 2 have centrosymmetric d imeric molecular structures in which the tin atoms are linked via the N ato ms of the NPPh3- groups. The tin atoms in 1 have a psi-tetrahedral coordina tion, those in 2 a trigonal-bipyramidal one. 1: Space group P1, Z = 1, lattice dimensions at -80 degrees C: a = 779.0(1) , b = 1080.1(1), c = 1170.4(1)pm, alpha = 64.49(1)degrees, beta = 88.42(1)d egrees, gamma = 79.13(1)degrees, R = 0.0293. 2: Space group P2(1)/n, Z = 2, lattice dimensions at -80 degrees C: a = 125 2.4(1), b = 1421.3(3), c = 1260.1(1) pm, beta = 108.50(1)degrees, R = 0.051 8.