REACTIONS OF SILYATED PHOSPHORANE IMINES WITH IODINE MONOCHLORIDE AND IODINE TRICHLORIDE - THE CRYSTAL-STRUCTURES OF [ME(3)SINPME(3)CENTER-DOT-ICL], [PH(3)PNCL-CENTER-DOT-ICL], AND [ME(3)PN(H)PME(3)][ICL2](2)

The donor-acceptor complex [Me(3)SiNPMe(3) . ICl] has been prepared from Me(3)SiNPMe(3) and ICl in acetonitrile solution forming yellow-orange crystals. [Ph(3)PNCl . ICl] can be prepared by the reaction of Me(3)SiNPPh(3) with ICl3 in dichloromethane solution forming pale yellow crystals. [Me(3)PN(H)PMe(3)][ICl2](2) is formed in a small amount by a slow reaction of Me(3)SiNPMe(3) with ICl3 in CCl4 suspension in the presence of traces of moisture. All samples are characterized by IR spectroscopy and by X-ray structure analyses. [Me(3)SiNPMe(3) . ICl] (1): Space group Iba2, Z = 8, structure solution with 1727 observed unique reflections, R = 0.051. Lattice dimensions at -60 degrees C: a = 1510.7, b = 1862.8, c = 988.9 pm. 1 has a molecular structure in which the N atom of the phosphorane imine is connected with the iodine atom of the ICI molecule in a linear arrangement N-I-Cl. Bond lengths N-I = 222.7 pm, I-Cl = 265.1 pm. [Ph(3)PNCl . ICl] (2): Space group Pna2(1), Z = 4, structure solution with 1530 observed unique reflections, R = 0.030. Lattice dimensions at 20 degrees C: a = 1522.8, b = 1408.3, c = 865.8 pm. 2 has a molecular structure in which the N atom of the N chlorophosphorane imine is connected with the iodine atom of the ICI molecule in a linear arrangement. Bond lengths N-CI = 174.4 pm, N-I = 229.5 pm, I-Cl = 251.2 pm. [Me(3)PN(H)PMe(3)][ICl2](2) (3): Space group P2(1)/c, Z = 4, structure solution with 1989 observed unique reflections, R = 0.029. Lattice dimensions at -50 degrees C: a = 1223.1, b = 1090.2, c = 1482.8pm, beta = 112.21 degrees. 3 consists of [Me(3)PN(H)PMe(3)](2+) ions and ICl2- anions. The PNP bond angle of the dication amounts to 134.4 degrees with PN distances of 165,6 and 166.1 pm, approximately according to double bonds.