A crucial role of adamantanoid Cu(II) complexes in the redox systems: CuCl–diallylsulfoxide–O2 and CuCl2–diallylsulfide–O2

The Cu4OCl6 core formation promotes oxidation of Cu(I) and diallylsulfide in the Cu(I)+diallylsulfoxide and Cu(II)+diallylsulfide systems, respectively, leading to the occurrence of different polymorphs in the above reactions. The polymorphic relationship is based on the symmetry homology: S4 ←Td →...

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Bibliographic Details
Published in:Polyhedron 2014-02, Vol.69, p.234-239
Main Authors: Olijnyk, V.V., Zarychta, B., Kinzhybalo, V.
Format: Article
Language:English
Subjects:
Diallylsulfide oxidation
O-body centered adamantanoid cage
Polymorphism
Structural homology
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Summary:The Cu4OCl6 core formation promotes oxidation of Cu(I) and diallylsulfide in the Cu(I)+diallylsulfoxide and Cu(II)+diallylsulfide systems, respectively, leading to the occurrence of different polymorphs in the above reactions. The polymorphic relationship is based on the symmetry homology: S4 ←Td → C3. The hypothetically reversible [Cu(I)(diallylsulfoxide)] ↔O2 [Cu(II)(diallylsulfide)] system was examined by FTIR spectroscopy and X-ray diffraction. It is stated that the Cu4OCl6 body centered adamantanoid cages, appearing at both the substrate and product sites, act as a template to promote the oxidation of diallylsulfide to diallylsulfoxide or Cu(I) to Cu(II), thus making the reaction irreversible. Each of these two adamantanoid cores possesses a different point symmetry as well as self assembly mode to form two polymorphs of the [Cu4OCl6(diallylsulfoxide)4] complex. Their polymorphic relationships based on the symmetry homology S4 ← Td → C3, as well as the distortion in the Cu(II) coordination geometry, are discussed.
ISSN:0277-5387
DOI:10.1016/j.poly.2013.11.040