Abstract
Naphthoquinonedithiolate (nqdt) is a “noninnocent” ligand forming dithiolene transition metal complexes. Most [M(nqdt)2]−1 and [M(nqdt)2]−2 complex ions are planar with each forming an isomorphous series with the (n-butyl)4N+ (tba) counter ion. The cobalt complex is isolated as a step dimer (tba)2[Co(nqdt)2]2 where two square-planar monomer units are bonded via Co−S intermolecular interactions.Ab initio andsemi-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 identify a more satisfactory counter ion. The magnetic susceptibilities of four complexes are discussed. The (tba)[Ni(nqdt)2] complex undergoes a weak ferromagnetic transition at 4.43 K while a mixed oxidation state Mn(II) complex exhibits a weak ferromagnetic transition at 40K. The crystal structures of (tba) [Cu(nqdt)2], (tba)[Ni(nqdt)2], (tba)2[Ni(nqdt)2], (tba)2[Pd(nqdt)2], {(tba)[Co(nqdt)2]}2 and four side reaction products 5,7,12,14-tetrahydrodibenzo-[b,i]thianthrene-5,7,12,14-tetraone (2), benzocyclohexa-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.
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Eduok, E.E., Krawiec, m., Buisson, YS.L. et al. Structure and properties of transition metal complexes of naphthoquinonedithiolate. J Chem Crystallogr 26, 621–638 (1996). https://doi.org/10.1007/BF01668623
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DOI: https://doi.org/10.1007/BF01668623