Preparation and Properties of trans-[CoCl2(tmd>)2]Cl, and trans- and cis-[Co(NCS)2(tmd)2]NO3 (tmd: Tetramethylenediamine)

Author： Nagata Kiyonori   Kanamori Kan  

Publisher： Taylor & Francis Ltd

ISSN： 0095-8972

Source： Journal of Coordination Chemistry, Vol.55, Iss.8, 2002-01, pp. : 925-932

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Abstract

The cobalt(III) complexes [CoX2(tmd)2]+ (X: Cl− or NCS−, tmd: tetramethylenediamine), in which tmd forms a seven-membered chelate ring, have been prepared. Trans-[CoCl2(tmd)2]Cl was derived from [Co(NO2)2(tmd)2]NO3 in a fairly good yield. Two geometrical isomers, trans and cis, of [Co(NCS)2-(tmd)2]NO3 were independently synthesized from trans-[CoCl2(tmd)2]Cl by different methods. The geometrical configurations of the isomeric pair of the NCS complex have been determined based on chromatographic behavior, electronic absorption spectra, and vibrational spectra. The d-d and CT absorption maxima of the NCS complex (18.7 × 103 cm−1 (ε = 275) and 30.9 × 103 cm−1 (ε = 3630) for the trans isomer, 19.3 × 103 cm−1 (ε = 302) and 31.0 × 103 cm−1 (ε = 4070) for the cis isomer) and the Co-N(amine) stretching frequency of trans-[CoCl2(tmd)2]Cl (418 cm−1) have been compared with those of the corresponding ethylenediamine and trimethylenediamine complexes.

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