A molecular box derived from cobaloxime units held together by 4-pyridinylboronic acid residues

The reaction of CH(3)Co(DH)(2)H(2)O with 4-pyridinyl boronic acid in methanol or water affords the dinuclear complexes [MeCo(DH)(DB(OR)(4-Py))](2), with R = Me (2) or H (3), respectively, through reaction of boron with the oxime oxygens of the alkylcobaloxime and coordination of the pyridinyl N to cobalt. The reaction is strongly pH dependent, and the formation of the complexes requires a neutral medium. The complexes have been fully characterized by (1)H and (13)C NMR spectroscopy, ESI-MS spectrometry, and elemental analysis. The X-ray structure shows that in 2, the pyridinyl groups are facing each other and nearly perpendicular both to the plane of the Co B Co1 B1 atoms and to the mean equatorial plane, so that the complex may be considered a molecular box. A dimeric arrangement has already been found in the related [MeCo(DH)(DB(OMe)(3-Py))](2) (1) complex, which forms a distorted molecular rectangle [Dreos, R.; Nardin, G.; Randaccio, L.; Tauzher, G.; Vuano, S. Inorg. Chem. 1997, 36, 2463]. The dimerization is possible in both cases, as the conformational freedom of the B bridge compensates for the different position (3- or 4-) of the pyridinyl N donor.