Mono- and Trinuclear Nickel(II) Complexes with Sulfur-Containing Oxime Ligands: Uncommon Templated Coupling of Oxime with Nitrile.

作者信息

Pavlishchuk Vitaly V., Kolotilov Sergey V., Addison Anthony W., Prushan Michael J., Butcher Raymond J., Thompson Laurence K.

机构信息

L. V. Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of the Ukraine, Prospekt Nauki 31, Kiev, 252039 Ukraine, Department of Chemistry, Drexel University, Philadelphia, Pennsylvania 19104, Department of Chemistry, Howard University, Washington, DC 20059, and Department of Chemistry, Memorial University, St. John's, NFD, Canada A1B 3X7.

出版信息

Inorg Chem. 1999 Apr 19;38(8):1759-1766. doi: 10.1021/ic981277r.

4,7-Dithiadecane-2,9-dione dioxime forms both violet and purple-black nickel(II) complexes with unexpected structural properties, quite unlike the square-planar chelates formed by its dithiaundecane homologue. Their perchlorate salts were isolated and examined crystallographically. The lilac product Ni{(Dtox)(CH(3)CNH)(2)}(2) entails a bis(iminoether) ligand formed by coupling of the dioxime with two moles of acetonitrile. The purple-black complex results from further ligand deprotonation, to yield trinuclear, antiferromagnetic Ni(3)(Dtox)(DtoxH)(2)(2).CH(3)CN, which maintains its structure in solution. The first one-electron electrochemical oxidation step is relatively facile for the trimer, yielding a Ni(2)(II)Ni(III) complex, whereas for Ni{(Dtox)(CH(3)CNH)(2)}(2) a transient Ni(I) species is accessible. Comment is made on those properties (coordination number, donor type, core charge) of nickel(II) coordination spheres that affect the accessibility of the corresponding nickel(I) and nickel(III) forms. Ni(3)(Dtox)(DtoxH)(2)(2).CH(3)CN crystallizes in the monoclinic space group P2(1)/n, with cell parameters a = 12.295(2) Å, b = 17.360(2) Å, c = 20.764(2) Å, alpha = 90 degrees, beta = 94.080(10) degrees, gamma = 90 degrees, V = 4420.7(6) Å(3), Z = 4. Ni{(Dtox)(CH(3)CNH)(2)}(2) crystallizes in the rhombohedral space group R&thremacr;, with cell parameters a = 32.954(2) Å, b = 32.954(2) Å, c = 13.477(2) Å, alpha = 90 degrees, beta = 90 degrees, gamma = 120 degrees, Z = 18.