COORDINATION CHEMISTRY OF 1,3-DITHIOLE-2-SELONE-4,5-DISELENOLATE (DSISE) AND 1,3-DITHIOLE-2-SELONE-4,5-DITHIOLATE (DMISE) - CRYSTAL AND MOLECULAR-STRUCTURE OF TETRABUTYLAMMONIUM BIS(1,3-DITHIOLE-2-SELONE-4,5-DISELENOLATO)NICKELATE(II) AND BIS(1,3-DITHIOLE-2-SELONE-4,5-DISELENOLATO)NICKELATE(III), [(N-C4H9)4N]2[NI(DSISE)2 AND (N-C4H9)4[NI(DSISE)2]

Syntheses and properties of metal(II) and metal(III) bis-chelates of 1,3-dithiole-2-selone-4,5-diselenolate (dsise), of the general type (BU4N)n[M(dsise)2] (n = 2 : M = Zn, Cd, Hg, Cu, Ni, Pd; n = 1 : M = Ni, Au) are reported and compared with chelates of the isologue 1,3-dichalcogenole-2-chalcogenone-4,5-dichalcogenolate (i.r., C-13-n.m.r., e.p.r., cyclovoltammetric data). The unexpected rearrangement during the syntheses of dsise and 1,3-dithiole-2-selone-4,5-diselenolate (dmise) is characterized by ab-initio SCF calculations. The x-ray structures of (Bu4N)2[Ni(dsise)2] (space group P2(1)/c, a = 8.5556(13) angstrom, b = 15.0009(12) angstrom, c = 19.696(3) angstrom, beta = 96.018(7)-degrees, V = 2513.9(5) angstrom 3, Z = 2) and Bu4N[Ni(dsise)2] (space group C2/c, a = 25.133(6) angstrom, b = 9.828(4) angstrom, c = 18.104(7) angstrom, beta = 132.81(1)-degrees, V = 3 281(2) angstrom 3, Z = 4) are given.