Complexes of tri-(2-pyridyl)amine. Part I. Complexes with cobalt(II), nickel(II), and copper(II) perchlorates

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Abstract
The ability of tri-(2-pyridyl)amine (tripyam) to function as a terdentate ligand is established by the preparation of Mo(CO)3(tripyam). The octahedral complexes Co(tripyam)2(ClO4)2, Ni (tripyam)2(ClO4)2, and Cu(tripyam)2(ClO4)2 have been prepared and X-ray powder results suggest the nickel and copper complexes to be isomorphous. The blue copper complex is readily isomerised to a yellow-green modification which has similar spectroscopic properties to [Cu (dppa)2(ClO4)2][dppa = di-(2-pyridyl)phenylamine] and is formulated as a complex of bidentate tri-(2-pyridyl)amine. Solid-state infrared spectra suggest the perchlorate groups to be co-ordinated in yellow-green [Cu(tripyam)2(ClO4)2] and in [Cu(dppa)2(ClO4)2] but not in the complexes [Cu(tripyam)2(ketone)2](ClO4)2(ketone = acetone or ethyl methyl ketone). [Cu(tripyam)2l, ClO4] and [Cu(tripyam)2l](ClO4) are isomers. [Cu(tripyam)2l2] and [Cu(tripyam)2(SCN)](ClO4) are also reported. Spectroscopic results for all complexes prepared are presented and briefly discussed.