Synthesis and structure of di-µ-oxo nitridotechnetium(VI) dimers and a monomeric nitridotechnetium(V) mixed-ligand complex

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Abstract
The di-µ-oxo technetium(VI) complexes [{TcN(S2CNEt2)}2(µ-O)2]1, [{TcN(S2CNC4H8)}2(µ-O)2]2, [AsPh4]2[{TcN(CN)2}2(µ-O)2]4 and [AsPh4]2[{TcN(edt)}2(µ-O)2]5(H2edt = ethane-1,2-dithiol) have been prepared either by reaction of [{TcN(OH2)3}2(µ-O)2]2+ or Cs2[TcNCl5] in Na4P2O7 solution with the appropriate ligand. The ESR spectra of solutions of 1 and 2 in SOCl2 and of 4 in MeCN with added AsPh4Cl·HCl showed that cleavage of the dimer occurs to give the nitridotechnetium(VI) monomers [TcNCl2(S2CNR2)](R = Et or R2= C4H8) or [TcNCl2(CN)2]–. Reaction of [TcVINCl2(S2CNEt2)] with K2[SCOCOS] gave the mixed-ligand complex [AsPh4][TcVN(S2CNEt2)(SCOCOS)]3. Single-crystal X-ray structures (Cu-Kα radiation) were determined for 1, 2 and 3. Complexes 1 and 2 are dimeric and are best described as two edge-sharing square pyramids, with TcN and Tc–Tc distances of 1.623(4), 1.624(4), 2.543(1), and 1.65(2), 1.59(2) and, 2.542(2)Å for 1 and 2 respectively. Complex 3 is monomeric with the technetium atom having a square pyramidal geometry, and a TcN distance of 1.54(2)Å.

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