Redox properties of N2S2-type nickel complexes with aromatic ligands. Crystal structure of [1,2-C6H4(SMe)NH2](2)Ni2+ (MeCN)(2)center dot 2ClO(4)(-)статья
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Дата последнего поиска статьи во внешних источниках: 18 июля 2013 г.
Аннотация:The redox properties of six chelate N(2)S(2)(_)type Ni((II)) complexes containing two aromatic NS or one N2S2 ligands, such as 2-aminothiophenol, 2-aminothiophenolate anion, 2-amido-thiophenolate dianion, 2-amidothioanisole, 2,2'-diaminodiphenyl disulfide dianion, and 8-quinolinethiolate anion, were studied by cyclic voltammetry at a glassy-carbon electrode in DMF. Some free ligands were also studied for comparison. A new Nil, complex with the 2,2'-diamidodiphenyl disulfide dianion was synthesized. The crystal and molecular structures including the square planar Ni(N2S2) center with two MeCN molecules as additional axial ligands were established for the Ni-II complex with 2-aminothioanisole [1,2-C6H4(SMe)NH2](2)Ni2+(MeCN)(2).2ClO(4)- using X-ray diffraction. The most part of the studied compounds are irreversibly oxidized and reduced; however, bis(2-amidothio-phenolato) nickel (iv) and bis(8-quinolinethiolato) nickel ((II)) show a quasi-reversible behavior in the reduction region. The electrochemically generated anionic form of the 8-thioquinoline complex is rapidly alkylated in the presence of (BuBr)-Br-n or (BuI)-I-n to form, probably, the corresponding butylnickel((III)) complex.