PHOSPHORANEIMINATO COMPLEXES OF IODINE - SYNTHESES AND CRYSTAL-STRUCTURES OF PH3PNIO2 AND PH3PNSIME3.I2

Ph3PNIO2 has been prepared as yellow crystals by the reaction of Ph3PN SiMe3 With I2O5 in boiling acetonitrile, whereas the molecular complex Ph3PNSiMe3 . I2 is formed as brown crystals by the reaction of Ph3PNS iMe3 with iodine in acetonitrile solution. Both complexes were charact erized by crystal structure determinations. Ph3PNIO,: Space group P2(1 )/n, Z = 4, 2858 observed unique reflections, R = 0.039. Lattice dimen sions at 19-degrees-C: a = 972.8(2), b = 1743.4(3), c = 1073.7(2) pm, beta = 115.46(3)-degrees. The compound forms monomeric molecules with pyramidal geometry at the iodine atom. The bond angle PNI (126.9-degre es) is unusually small; the PN bond length of 159.2 pm corresponds wit h a double bond. Ph3PNSiMe3 . I2: Space group P1BAR, Z = 2, 3560 obser ved unique reflections, R = 0.033. Lattice dimensions at 19-degrees-C: a = 941.2(2), b = 1 041.7(2), c = 1 287.4(3) pm, alpha = 78.34(1)-deg rees, beta = 72.00(2)-degrees, gamma = 86.08(2)-degrees. The compound forms monomeric molecules, in which the I2 molecule and the nitrogen a tom of the phosphoraneimine molecule realize a linear N-I-I axis with a bond length N-1 of 243.2 pm.