Mixed-spin binuclear nickel(II) complexes in unsymmetrical ligand environments and related mononuclear compounds: electronic and molecular structures in solution and in the solid state.

Nickel(II) complexes of three new heterodonor ligands (HL(1), H(2)L(2), and H(3)L(3)) based on 2-aminocyclopent-1-ene-1-dithiocarboxylate have been synthesized, and their crystallographic characterizations are reported. With the pentacoordinating ligands HL(1) and H(3)L(3), the products obtained (1 and 2) are both mononuclear square planar compounds in which one of the pyrazolyl arms of ligand HL(1) and the bridgehead alkoxy oxygen of H(3)L(3) are staying away from coordination in 1 and 2, respectively. The saturated three carbon alkanyl chain in the ligand H(3)L(3) provides enough flexibility to generate tetrahedral distortion (dihedral angle, 22.7 degrees ) in the planarity of 2. Compound 1 displays paramagnetic line-broadening in its (1)H NMR spectrum due to oligomerization in solution. With the unsymmetrical binucleating ligand H(2)L(2), two mixed-spin homodinuclear complexes (3 and 4) have been synthesized using pyrazole and 2-mercaptopyridine as ancillary mu(2)-bridging ligands. Both these complexes have square planar low-spin and spin-triplet nickel(II) centers which display both coordination number and donor set asymmetry in tandem. The compounds have been characterized by (1)H NMR, electronic spectroscopy, and electrochemical studies.