COORDINATION COMPOUNDS OF THALLIUM(3) .3. VIBRATIONAL SPECTRA OF SEVERAL ANIONIC AND NEUTRAL COMPLEXES OF THALLIUM(3) CHLORIDE AND IODIDE AND NATURE OF THESE SPECIES IN SOLID STATE AND IN POLAR SOLVENTS

Several new anionic and neutral complexes of thallium(III) chloride and iodide have been prepared. These include (C2H5)4-NTICI3I, (C2H3)4NTlCl4B, TlCl3·1.5pyz, (T1X3)2·terpy, TlC3 · terpy, and TlI3·py, where X = Cl or I, B = 2,2′-bipyridyl or 1,10-phenaπthroline, pyz = pyrazine, terpy = 2,2′,2″-terpyridyl, and py = pyridine. Molecular weight measurements in acetone and acetonitrile show that these and other complexes of thallmm(III) [TlCl3·2py, TlCl3·3γ-pic, and TlCl3· 2DMSO] are appreciably dissociated in polar media. TlCl3 · 3γ-pic, TlCl32py, TlCl3·2DMSO, and TlX3-·bipy behave as weak electrolytes in these two solvents, whereas (TlX3)2 · terpy are typical 1:1 electrolytes. The above solution data together with the far-infrared and Raman (for TlCl3I− and TlCl3·2DMSO) spectra of the solid complexes indicate the structures: TlCl3X−(X = Br or I), pseudo-tetrahedral; TlX4B−(X = Cl or Br, B = bipyorphen), cis-MX4L2 type structure; TICl3· 3γ-pic, cis-TlCl3X3; TlCl3 ·l.5pyz, trans-TlCl3N3; (TlX3)2-terpy, [TlX2 ·terpy] +[TlX4]− TlCl3·2DMSO, trans-trigonal bipyramid; TlCl3 ·2py, TlCl3 ·bipy, and TlCl3 ·phen, halogen-bridged dimers or polymers. Comparisons are made where pos¬sible with the analogous indium(III) halide systems. © 1968, American Chemical Society. All rights reserved.