Complexation of the new tetrakis[methyl(diphenylphosphorylated)] cyclen derivative with transition metals: First examples of octacoordinate zinc(II) and cobalt(II) complexes with cyclen moleculesстатья

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Дата последнего поиска статьи во внешних источниках: 10 августа 2018 г.

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[1] Complexation of the new tetrakis[methyl(diphenylphosphorylated)] cyclen derivative with transition metals: First examples of octacoordinate zinc(ii) and cobalt(ii) complexes with cyclen molecules / G. S. Tsebrikova, I. N. Polyakova, V. P. Solov'ev et al. // Inorganica Chimica Acta. — 2018. — Vol. 478. — P. 250–259. The new tetrakis[methyl(diphenylphosphorylated)] cyclen derivative DOTMPPh2 is synthesized and its complexation with cobalt(II), nickel(II), copper(II), and zinc(II) perchlorates is studied. According to the X-ray diffraction data, isostructural compounds [Zn(DOTMPPh2)](ClO4)2.2.66CH3CN.0.34H2O and [Co(DOTMPPh2)](ClO4)2.2.72CH3CN.0.28H2O provide the first examples of octacoordinate Zn2+ and Co2+ complexes with cyclen molecules. The coordination polyhedra of M2+ atoms are distorted Archimedean antiprisms formed by four cyclen N atoms and four phosphoryl O atoms. In [Cu(DOTMPPh2)](ClO4)2 the polyhedron of the copper atom is a slightly distorted tetragonal pyramid with four nitrogen atoms at the base and the O atom of a phosphoryl group at the apical vertex. The IR spectral data suggest that in the solid state Ni 2+ complex with DOTMPPh2 has an octahedral structure, and it was confirmed by the high-spin magnetic moment of the complex. According to the UV–vis data, the structures of Cu2+, Ni2+, and Co2+ complexes in solution are close to those in the solid state. The stability constants of Cu2+, Ni2+, and Co2+ complexes with DOTMPPh2 in ethanol and acetonitrile are estimated from UV–vis spectrophotometric data. The log K values for the M2+ + L = (M2+)L reaction in acetonitrile increase in the (Co2+)L < (Ni2+)L < (Cu2+)L order (4.56, 5.10, and 5.85, respectively). The stability of complexes in MeCN is slightly higher than in EtOH. In MeCN solution, complex (Cu2+)2L is found along with (Cu2+)L. [ DOI ]

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