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Synthesis and characterization of cobalt(ii) complexes with tripodal polypyridine ligand bearing pivalamide groups. Selective formation of six- and seven-coordinate cobalt(ii) complexes†
Jun Matsumoto,Tatsuya Suzuki,Yuji Kajita,Hideki Masuda
Dalton Transactions Pub Date : 02/03/2012 00:00:00 , DOI:10.1039/C2DT12056A
Abstract

The reactions of CoX2 (X = Cl, Br, I and ClO4) with the tripodal polypyridine N4O2-type ligand bearing pivalamide groups, bis(6-(pivalamide-2-pyridyl)methyl)(2-pyridylmethyl)amine ligand (H2BPPA), afforded two types of Co(II) complexes as follows. One type is purple-coloured Co(II) complexes, [CoCl2(H2BPPA)] (1Cl) and [CoBr2(H2BPPA)] (1Br) which were prepared when X = Cl and Br, respectively. The other type is pale pink-coloured Co(II) complexes, [Co(MeOH)(H2BPPA)](ClO4)2 (2·(ClO4)2) and [Co(MeCN)(H2BPPA)](I)2 (2·(I)2), which were obtained when X = I and ClO4, respectively. From the reaction of 1Cl and NaN3, a purple-coloured complex, [Co(N3)2(H2BPPA)] (1azide), was obtained. These Co(II) complexes were characterized by X-ray structural analysis, IR and reflectance spectroscopies, and magnetic susceptibility measurements. All these Co(II) complexes were shown to be in a d7 high-spin state based on magnetic susceptibility measurements. The former Co(II) complexes revealed a six-coordinate octahedron with one amine nitrogen, three pyridyl nitrogens, and two counter anions, and one coordinated anion, Cl, Br and N3, forming intramolecular hydrogen bonds with two pivalamide N–H groups. On the other hand, the latter Co(II) complexes showed a seven-coordinate face-capped octahedron with one amine nitrogen, three pyridyl nitrogens, two pivalamide carbonyl oxygens and MeCN or MeOH. In these structures, intramolecular hydrogen bonding interaction was not observed, and the metal ion was coordinated by the pivalamide carbonyl oxygens and solvent molecule instead of the counter anions. The difference in coordination geometries might be attributable to the coordination ability and ionic radii of the counteranions; smaller strongly binding anions such as Cl, Br and N3 gave the former complexes, whereas bulky weakly binding anions such as I and ClO4 afforded the latter ones. In order to demonstrate this hypothesis, the small stronger coordinating ligand, azide, was added to complexes 2·(ClO4)2 to obtain the dinuclear cobalt(II) complex in which two six-coordinate octahedral cobalt(II) species were bridged with azide, 3·(ClO4). Also, the abstraction reaction of halogen anions from complexes 1Cl by AgSbF6 gave a pale pink Co(II) complex assignable to 2·(SbF6)2.

Graphical abstract: Synthesis and characterization of cobalt(ii) complexes with tripodal polypyridine ligand bearing pivalamide groups. Selective formation of six- and seven-coordinate cobalt(ii) complexes
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