Mikhail A. Vershinin

Structure of the product of free-radical substitution of chlorine atoms in iron(II) clathrochelate with two ethanol fragments

The homolytic substitution of chlorine atoms afforded iron(II) clathrochelate bearing two ethanol fragments. The structure of the compound was determined by XRD in the crystalline state and by NMR in solution.

Two alternative approaches to modification of a cage complex: nucleophilic substitution and electrophilic addition for the synthesis of an iron(II) clathrochelate with an annulated imidazole fragment

A rib-functionalized iron(II) tris-dioximate clathrochelate bearing an annulated phenylimidazole fragment was prepared using nucleophilic substitution and electrophilic addition at the chelating α-dioximate fragment of the macrobicyclic framework. The resultant cage complex was identified with single crystal XRD, analytical data, 1H, 13C, 19F, 11B NMR spectroscopy, and examined with UV–vis spectroscopy and CVA. Two approaches to modification of the clathrochelate framework are compared. Graphical abstract

Iron(II) clathrochelate with an annelated 4,5-dimercapto-[1,3]dithiol-2-thione moiety: Synthesis, structure, and redox reactions

Nucleophilic substitution of chlorine atoms in iron(II) dichloroclathrochelate induced by 4,5-dimercapto-[1,3]dithiol-2-thione dianion gave rise to a cage complex with an annelated sulfur-containing heterocyclic moiety. The composition and structure of this complex were determined by X-ray crystallography and multinuclear NMR spectroscopy in a crystal and in solution, respectively; cyclic voltammetry (CVA) and EPR were used to study the redox reactions of the complex in solution to yield a ligand-centered radical-anionic product.

Structure of the product of 1,8-diazabicyclo[5.4.0]undecane-7-ene substitution for chlorine atoms in dichlorine substituted Fe(II) clathrochelate

Methods of X-ray diffraction analysis and nuclear magnetic resonance are used to determine the molecular structure of macrobicyclic boron-capped tris-dioxymate iron(II) clathrochelate containing an annellated 5-membered heterocycle.

Features of strong O–H⋯O and N–H⋯O hydrogen bond manifestation in vibrational spectra

The work deals with the establishment of the dependence of the vibrational frequencies of strong O–H⋯O and N–H⋯O hydrogen bonds for the diagnosing the bonds themselves. To this end, the Raman spectra of a large number of different normal and deutero-substituted crystals characterized by the presence of strong O–H⋯O and N–H⋯O bonds are measured and the quantum chemical calculation is performed for one of these compounds. The dependence of the O–H stretching frequency on the O⋯O distance is constructed differing from that previously known for short O⋯O contacts. The mechanisms of significant broadening of the O–H vibration band in strong O–H⋯O hydrogen bonds are considered. Different dependences of the N–H vibrational frequencies in N–H⋯O bonds are reported and the causes of this diversity are discussed.

Structure of a product of free radical substitution of a chlorine atom for 1,3,5-trioxane in an iron(II) chlathrochelate

A tert-BuOOH/Fe(II) system is used for the free radical substitution of the chlorine atom at the rib of a boron capped iron(II) tris-dioximate chlathrochelate for 1,3,5-trioxane. The structure of the compound is determined by single crystal XRD and solution NMR.