SYNTHESIS AND CHARACTERIZATION OF TETRABUTYLAMMONIUM (2-AMINOBENZENETHIOLATO(2-)-S,N)TETRACHLOROTECHNETATE(V)

The reaction of (n-Bu4N)[TcO(abt)2] (abt = 2-aminobenzenethiolato(2-)-N,S) with 12 M HCl in methanol gives the blue Tc(V) compound (n-Bu4N)[TcCl4(abt)]. Magnetic susceptibility measurements reveal this compound to have two unpaired electrons. This indicates that the ligand, with one hydrogen per nitrogen, is doubly anionic, establishing the metal oxidation state of +5. Infrared data show a single N-H stretching frequency at 3254 cm-1. An X-ray crystal structure of (n-Bu4N)[TcCl4(abt)] is also reported. Crystal data for C22H41N2SCl4Tc: triclinic, space group P1BAR (No. 2), a = 11.5154 (8) angstrom, b = 13.6200 (9) angstrom, c = 10.5547 (8) angstrom, alpha = 95.205 (5)-degrees, beta = 116.970 (7)-degrees, gamma = 76.198 (4)-degrees, and V = 1423.5 (4) angstrom 3 to give Z = 2 for D(calc) = 1.401 g/cm3. The structure solution and refinement based on 6893 reflections converged at R = 0.047 and R(w) = 0.048.