Preparation and structural characterization of 4-pyridylboron-capped iron(II) clathrochelates and their chemical transformations into hybrid metallo(IV)phthalocyaninatoclathrochelate derivativesстатья
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Аннотация:Mixed boron,antimony-capped iron(II) tris-dioximate monoclathrochelates and their
hybrid phthalocyaninatoclathrochelate derivatives, the molecules of which are decorated with the single
N-donor 4-pyridyl group, were obtained using two different approaches, such as (i) a transmetallation
(a capping group exchange) reaction of their antimony-capped macrobicyclic precursors, and (ii) the
direct template condensation of the Fe2+ ion as a matrix. The obtained complexes were characterized
using elemental analysis, 1H and 13C{1H} NMR, MALDI-TOF MS, and UV–vis spectra, and by
the single-crystal X-ray diffraction experiments. Solution UV-vis spectra of 4-pyridyl-terminated
iron(II) phthalocyaninatoclathrochelates can be described as a superposition of the spectrum of its
metallocomplex precursor MIVPc and that of the iron(II)-encapsulating semiclathrochelate fragment.
As follows from the X-ray diffraction data for the hybrid hafnium(IV)-capped tris-dimethylglyoximate
pthalocyaninatoclathrochelate and its macrobicyclic boron,antimony-capped precursor, their FeN6-
coordination polyhedra possess the geometry close to intermediate between a trigonal prism (TP) and
a trigonal antiprism with the distortion angles j of 20–30°. Due to a non-equivalence of their capping
fragments, it can be also described as a distorted truncated trigonal pyramid. ZrN4O3-coordination
polyhedron in the hybrid complex possesses the geometry of a capped TP. 4-Pyridylboron-capped
pthalocyaninatoclathrochelates are proposed as prospective monodentate N-donor 3D-ligands for the
design of various clathrochelate-based coordination assemblies, polytopic and polynuclear systems.