X-ray fluorescent spectroscopy study of the charge state of heteroatoms in organic compounds of third row elements. 6. Realationship between SK? shifts and magnitudes of charges on the sulfur atoms, determined from quantum chemical calculations

Bis(carboranyl)amides 1,1′-μ-(CH2NH(O)C(CH2)n-1,2-C2B10H11)2 (n = 0, 1) were prepared by the reactions of the corresponding carboranyl acyl chlorides with ethylenediamine. Crystal molecular structure of 1,1′-μ-(CH2NH(O)C-1,2-C2B10H11)2 was determined by single crystal X-ray diffraction. Treatment of bis(carboranyl)amides 1,1′-μ-(CH2NH(O)C(CH2)n-1,2-C2B10H11)2 with ammonium or cesium fluoride results in partial deboronation of the ortho-carborane cages to the nido-carborane ones with formation of [7,7′(8′)-μ-(CH2NH(O)C(CH2)n-7,8-C2B9H11)2]2−. The attempted reaction of [7,7′(8′)-μ-(CH2NH(O)CCH2-7,8-C2B9H11)2]2− with GdCl3 in 1,2-dimethoxy- ethane did not give the expected metallacarborane. The stability of different conformations of Gd-containing metallacarboranes has been estimated by quantum-chemical calculations using [3,3-μ-DME-3,3′-Gd(1,2-C2B9H11)2]− as a model. It was found that in the most stable conformation the CH groups of the dicarbollide ligands are in anti,anti-orientation with respect to the DME ligand, while any rotation of the dicarbollide ligand reduces the stability of the system. This makes it possible to rationalize the design of carborane ligands for the synthesis of gadolinium metallacarboranes on their base.

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Development of Prediction Models for the Reactivity of Organic Compounds with Ozone in Aqueous Solution by Quantum Chemical Calculations: The Role of Delocalized and Localized Molecular Orbitals

Environmental Science & Technology ◽

10.1021/acs.est.5b00902 ◽

2015 ◽

Vol 49 (16) ◽

pp. 9925-9935 ◽

Cited By ~ 43

Author(s):

Minju Lee ◽

Saskia G. Zimmermann-Steffens ◽

J. Samuel Arey ◽

Kathrin Fenner ◽

Urs von Gunten

Keyword(s):

Aqueous Solution ◽

Quantum Chemical Calculations ◽

Organic Compounds ◽

Quantum Chemical ◽

Prediction Models ◽

Molecular Orbitals ◽

Localized Molecular Orbitals

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Electrochemical aromatization of dihydroazines. Effect of chalcogenophosphoryl (CGP) substituents on anodic oxidation of 9-CGP-9,10-dihydroacridines

Synthesis ◽

10.1055/a-1521-3166 ◽

2021 ◽

Author(s):

Alexander Schepochkin ◽

Oleg N. Chupakhin ◽

Nadezhda Demina ◽

Maxim Averkov ◽

Tatyana Shimanovskaya ◽

...

Keyword(s):

Cyclic Voltammetry ◽

Structural Analysis ◽

Quantum Chemical Calculations ◽

Anodic Oxidation ◽

Quantum Chemical ◽

X Ray

The effect of chalcogenophosphoryl fragments on the anodic oxidation of 9-chalcogenophosphoryl-9,10-dihydroacridines was studied in detail. The data of X-ray structural analysis, quantum chemical calculations and cyclic voltammetry obtained for these compounds provide an explanation of the observed features. The direct electrochemical phosphorylation of acridine was first carried out successfully.

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