The synthesis and structural characterization of the bifunctional chelating ligands:  4,5-dithiocatechol, (H2DTC), 4,5 dithio-ortho-quinone (H2DTQ) and the tetrathio, (TTT2-  ), 1,1-dithio, (c-DTT2-) and 1,4 dihio-terephthalate (t-DTT2-) ligands are described.  The unique coordination properties of these ligands allow for the synthesis of homo- and heteronuclear polymers.  Dramatic color changes accompany the addition of �hard� Lewis acids (SnIV, AlIII and SbIII) to the structurally characterized, S-coordinated square [M(DTC)2]2- (M = Ni(II) , Cu(II)) and the corresponding  DTQ complexes.  The heteronuclear complexes are similar to those obtained previously using the   dithiooxalate complexes as ligands for hard Lewis acids.  The reaction of (Ph4P+)2TTT with CuCl  gives the  (Ph4P+)2{TTT (S2-TTT)(CuCl)2} with trigonal S2CuCl sites where both dithioacid units  have undergone ring expansion by S addition.  With the (Ph4P+)2(c-DTT) ligand, reaction with CuCl gives  (Ph4P+)[(S-DTT)(CuCl)]  which contains a free carboxylate group. With c-DTT2- a crystalline Ni/Zn polymer is obtained and contains chains of L3NiZn2.  With S6- coordinated Ni(II) and O6-coordinated Zn(II) ions arranged in stacked layers.  The Ph4P+ salt of the t--- -- DTT2- ligand gives a crystalline homometallic polymer with Cu(I) which upon treatment with triphenylphosphine gives  polymeric ,structurally characterized ,{(t-DTT-Cu(I)-PPh3P)}-x chains with Ph4P+ as counterions.  In these chains the S2Cu(I)P centers are   trigonal planar.  The coordination chemistry and use of these ligands in the syntheses of heterometallic extended lattices will be discussed.

Heterometallic coordination polymers with bifunctional chelating ligands

244th National Meeting (2012)

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