Studies of technetium complexes. 9. Use of the tetrachloronitridotechnetate(VI) anion for the preparation of nitrido complexes of technetium. Crystal structure of bis(8-quinolinethiolato)nitridotechnetium(V)

The Tc/sup VI/NCl/sub 4//sup -/ anion is shown to be a useful intermediate for the preparation of Tc identical with N complexes. Reaction of AsPh/sub 4/(TcNCl/sub 4/) with LiBr in acetone gives AsPh/sub 4/(TcNBr/sub 4/), and reaction of TcNCl/sub 4//sup -/ with CsCl gives Cs/sub 2/(TcNCl/sub 5/). The TcNCl/sub 4//sup -/ anion undergoes reduction on reaction with PPh/sub 3/, KNCS, Na(S/sub 2/CNEt/sub 2/), and 8-quinolinethiol(C/sub 9/H/sub 6/NSH) to give the Tc/sup V/ identical with N complexes (TcNCl/sub 2/(PPh/sub 3/)/sub 2/), (NEt/sub 4/)/sub 2/(TcN(NCS)/sub 4/(CH/sub 3/CN)), (TcN(S/sub 2/CNEt/sub 2/)/sub 2/), and (TcN(C/sub 9/H/sub 6/NS)/sub 2/), respectively. A single-crystal X-ray structure determination of bis(8-quinolinethiolato)nitridotechnetium(V), (TcN(C/sub 9/H/sub 6/NS)/sub 2/), is reported. Crystals are monoclinic, space group C2/c, with a = 15.92 (1) A, b = 7.347 (6) A, c = 15.33 (2) A, ..beta.. = 110.89 (8)/sup 0/, and Z = 4. Full-matrix least-squares refinement gave R = 0.029 for 1618 independent reflections. The coordination geometry of technetium is distorted square pyramidal with the apical Tc identical with N bond of length 1.623 (4) A. Tc-S and Tc-N(quinoline) bond distances are 2.3559 (7) and 2.135 (2) A, respectively. 27 references, 1 figure, 2 tables.