STRUCTURE AND PROPERTIES OF TRANSITION-METAL COMPLEXES OF NAPHTHOQUINONEDITHIOLATE

Naphthoquinonedithiolate (nqdt) is a ''noninnocent'' ligand forming di thiolene transition metal complexes. Most [M(nqdt)(2)](-1) and [M(nqdt )2](-2) complex ions are planar with each forming an isomorphous serie s with the (n-butylN+ (tba) counter ion. The cobalt complex is isolate d as a step dimer (tba)(2)[Co(nqdt)2](2) where two square-planar monom er units are bonded via Co-S intermolecular interactions. Ab initio an d semi-empirical calculations are used to investigate the complex ions . The complexes form tba single crystals only with difficulty, and an extensive study with ions of various shapes and charges failed to iden tify a more satisfactory counter ion. The magnetic susceptibilities of four complexes are discussed. The (tba)[Ni(nqdt)(2)] complex undergoe s a weak ferromagnetic transition at 4.43 K while a mixed oxidation st ate Mn(II) complex exhibits a weak ferromagnetic transition at 40K. Th e crystal structures of (tba) [Cu(nqdt)(2)], (tba)[Ni(nqdt)(2)], (tba) (2)[Ni(nsdt)(2)], (tba)(2)[Pd(nqdt)(2)], {(tba)[Co(nqdt)(2)]}(2) and f our side reaction products rahydrodibenzo-[b,i]thianthrene-5,7,12,14-t etraone (2), ocyclohexa-2,5-diene-1,4-dione-1,3-thiole-2-thione (3), a thiomethyl derivative (4), and an unusual oxidatively coupled product (5) are reported.