ic4011746_si_002.cif (23.93 kB)

Synthesis and Oxidative Reactivity of 2,2′-Pyridylpyrrolide Complexes of Ni(II)

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posted on 19.08.2013 by Nikolay P. Tsvetkov, Chun-Hsing Chen, José G. Andino, Richard L. Lord, Maren Pink, René W. Buell, Kenneth G. Caulton
Synthesis and characterization of divalent nickel complexed by 2-pyridylpyrrolide bidentate ligands are reported, as possible precursors to complexes with redox active ligands. Varied substituents on the pyrrolide, two CF3 (L2), two tBu (L0), and one of each type (L1) are employed and the resulting Ni­(Ln)2 complexes show different Lewis acidity toward CO, H2O, tetrahydrofuran (THF), or MeCN, the L2 case being the most acidic. Density functional theory calculations show that the frontier orbitals of all three Ni­(Ln)2 species are localized at the pyrrolide groups of both ligands and Ni­(Ln)2+ can be detected by mass spectrometry and in cyclic voltammograms (CVs). Following cyclic voltammetry studies, which show electroactivity primarily in the oxidative direction, reactions with pyridine N-oxide or Br2 are reported. The former yield simple bis adducts, Ni­(L2)2(pyNO)2 and the latter effects electrophilic aromatic substitution of the one pyrrolide ring hydrogen for both chelates, leaving it brominated.