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
Информация о цитировании статьи получена из
Web of Science,
Scopus
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 10 августа 2018 г.
Аннотация: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.