The reaction of hexamethylenetetramine (CH2)6N4 with sparingly soluble (1-hydroxyethylidene)diphosphonates M(H2L)•2H2O (M = Mn, Co, Zn; H4L is (1-hydroxyethylidene)diphosphonic acid) afforded water-soluble compounds of the composition [(CH2)6N4H2]ML•2H2O (M = Mn (1), Co (2), Zn (3)). Manganese derivative 1 lost its solubility during storage, whereas the cobalt and zinc compounds retained it. The tetrafunctional base hexamethylenetetramine reacts with tetrafunctional (1-hydroxyethylidene)-diphosphonic acid H4L in methanol to form hexamethylenetetraminium (1-hydroxyethylidene)diphosphonate dihydrate [(CH2)6N4H]+(H3L)•2H2O (4). When heated in an aqueous methanol medium, compound 4 dissociates to acid H4L and base (CH2)6N4, hexamethylenetetramine reacts with water to produce ammonia and formaldehyde, and the acid H4L and ammonia generate diammonium (1-hydroxyethylidene)diphosphonate (NH4)2H2L. The heating in an inert atmosphere causes the extensive decomposition of compound 4 giving a non-volatile water-soluble residue and a series of volatile organic compounds, such as amines, amides, amino alcohols, and amino acids. The obtained compounds were studied by IR spectroscopy, elemental analysis, powder X-ray diffraction, and thermogravimetric analysis. The molecular structure of diammonium (1-hydroxyethylidene)diphosphonate (NH4)2H2L was determined.

The literature data on melting points (Tm) of silicon, germanium, tin, and lead compounds of 26 narrow series has been analyzed. The considered compounds form weak intermolecular complexes, which leads to the appearance of the polarizability effect. Using the correlation analysis, it was established for the first time that the Tm values depend on the combined influence of the inductive, resonance, polarizability, and steric effects of substituents. The contribution of the polarizability effect reaches 65

The published data on the substituent influence on the boiling points T b for 19 series of boron, aluminium, silicon, germanium, tin, and phosphorus compounds were considered using correlation analysis. It was established for the first time that the T b values depend not only on the classical (inductive, resonance, and steric) effects, but also on the polarizability effect of substituents. In some series, the polarizability effect has a major influence on T b .

A series of 4-hydroxy-4,9-dihydro-4H-xanthen-4-one derivatives were synthesized using the oxidative cyclization reaction of space-shielded catecholphenols. The structure of 1,3,5,7-tetra-tert-butyl-4a,8-dihydroxy-9H-xanthen-4(4aH)-one was determined by X-ray diffraction analysis (CCDC 2345899). The antiradical properties of new compounds were studied by their reaction with 2,2-diphenyl-1-picrylhydrazyl (DPPH radical).

Literature data have been considered from the viewpoint of the influence of substituents on the mole specific heats Cp at constant pressure for 14 series of organic compounds. Using the correlation-analysis method, it has been shown for the first time that experimental and calculated Cp values depend not only on the inductive, resonance, and steric influence, but also on the polarization effect of variable substituents associated with a constant reactive center. In individual cases the polarization effect has the most significant impact on Cp.

Water insoluble calcium hydroxide Ca(OH)2 or calcium carbonate CaCO3 react with aqueous solution of (1-hydroxyethylidene)diphosphonic acid and nitrilotrimethylenephosphonic acid to form poorly soluble calcium (1-hydroxyethylidene)diphosphonate trihydrate and calcium nitrilotrimethylenephosphonate trihydrate, respectively. The reaction of calcium chloride CaCl2 with the disodium salt of ethylenediaminetetraacetic acid afforded poorly soluble calcium ethylenediaminetetraacetate hexahydrate. The reaction of suspensions of complexes of (1-hydroxyethylidene)calcium diphosphonate trihydrate, calcium ethylenediaminetetetraacetate hexahydrate and calcium nitrilotrimethylenephosphonate trihydrate with 2-aminoethanol led to the formation of water-soluble (1-hydroxyethylidene)bis(2-aminoethanol)calcium diphosphonate, tris(2-aminoethanol)calcium nitrilotrimethylenephosphonate, and bis(2-aminoethanol)calcium ethylenediaminetetraacetate, respectively. The molecular structure of calcium ethylenediaminetetraacetate hexahydrate was characterized by single-crystal X-ray diffraction method.

A series of sterically hindered catecholphenols was synthesized by the reaction 4,6-di-tert-butyl-3-methoxymethylcatechol with resorcinol, 4,6-di-tert-butylresorcinol, orcinol, 3,5-dimethoxyphenol, α- and β-naphthol. The structure of the obtained compounds was proved by NMR, IR and mass spectroscopy. The structure of 4,6-di-tert-butyl-3-[(2-hydroxynaphthalen-1-yl)methyl]benzene-1,2-diol was determined by single-crystal X-ray diffraction. The radical scavenging of obtained compounds were determined using 2,2-diphenyl-1-picrylhydrazyl radical test.

The published data on the enthalpy of sublimation Δ H sub for 13 series of organic and metal-organic compounds are considered using the correlation analysis. Each series has a fixed reaction center and variable substituents. It is shown for the first time that Δ H sub values depend not only on the classical inductive, resonance, and steric effects, but also on the polarization effect of substituents. In some series, the polarization effect has a major influence on Δ H sub .

Di- tert -alkyl-substituted catechols with a heterocyclic imidazole-type substituent were synthesized in three steps from catecholaldehydes. The 1,1,4,4-tetramethylbutanediyl substituent was shown to be resistant to the action of acids in the demethylation reaction. The isomerization of 3,4,5-substituted catechols to the 3,4,6-substituted isomers was observed. The molecular structures of the synthesized compounds in the crystalline state were established by X-ray diffraction analysis. For the catechol derivatives, the tertiary substituent in the ortho position to the imidazole moiety was shown to have an effect on the mutual arrangement of the catechol and heterocyclic moieties. The electrochemical properties of the synthesized imidazole-containing catechols were studied and their anti-radical activity was evaluated by the 2,2-diphenyl-1-picrylhydrazyl assay.

Методом корреляционного анализа рассмотрены литературные данные по энтальпиям сублимации DHsub0 для 14 серий органических и металлорганических соединений. Каждая серия имеет фиксированный реакционный центр и варьируемые заместители. Впервые показано, что значения DHsub0 зависят не только от классических индуктивного, резонансного и стерического эффектов, но и от поляризационного эффекта заместителей. В некоторых сериях поляризационный эффект оказывает основное влияние на DHsub0

The review summarizes the data on the dependence of the properties of compounds of the silicon subgroup elements on the reactive site and substituents. When an excess charge appears at the reactive site, the properties of compounds and their complexes depend not only on the inductive and resonance effects, but also on the polarization effect of the substituents. In certain cases, the polarization effect has a predominant effect on the properties.

Literature data on the solubility (Sol) and Gibbs energy of dissolution (ΔG°) reported for 26 series of derivatives of benzene, pyridine, and fluorocarbons in various solvents were considered using correlation analysis. An excess charge appears on the reaction center due to the formation of weak solute—solvent complexes, which results in the manifestation of polarizability effect. It was established for the first time that the values of Sol and ΔG° depend on the joint influence of inductive, resonant, polarization, and steric effects of substituents, whereas contribution of the polarizability effect reaches 50%.

Проведен сравнительный анализ экспериментальных и теоретических колебательных спектров в диапазоне частот 700—100 см–1 для моно-о-иминосемихиноновых комплексов олова(IV) c общей формулой LSnR2Cl (1—5) и LSnR3 (6, 7) (L — анион-радикал 4,6-ди-трет-бутил-N-(2,6-ди-изо-пропилфенил)-о-иминобензохинона, R = Me (1, 6), Et (2), n-Bu (3), t-Bu (4), Ph (5, 7)). Установлено, что для изученных соединений полосы поглощения валентных колебаний ν(Sn—O) и ν(Sn—N) находятся в интервалах 460—360 см–1 и 340—350 см–1 соответственно. Положение полосы поглощения ν(Sn—O) обусловлено с длиной связи Sn—O. В частности, удлинение указанной связи на 0.2 Å в комплексе 6 по сравнению с остальными соединениями приводит к смещению полосы на 20 см–1 в длинноволновую область спектра. Показано, что параметры ν(Sn—O), a(117, 119Sn) и длины связей d(Sn—O), d(Sn—N) и d(Sn—C) в комплексах зависят от четырех эффектов заместителей, связанных с атомом олова: индуктивного, резонансного, поляризационного и стерического.

We report a comparative analysis of experimental and theoretical vibrational spectra recorded in the frequency region of 700-100 cm–1 for mono-o-iminosemiquinone tin(IV) complexes with general formulas LSnR2Cl (1-5) and LSnR3 (6, 7) (L is the 4,6-di-tert-butyl-N-(2,6-di-iso-propylphenyl)-o-iminobenzoquinone radical anion, R = Me (1, 6), Et (2), n-Bu (3), t-Bu (4), Ph (5, 7)). It is established that absorption bands of ν(Sn–O) and ν(Sn–N) stretching vibrations in the studied compounds occur at 460-360 cm–1 and 340-350 cm–1, respectively. The position of the ν(Sn–O) absorption band correlates with the Sn–O bond length. In particular, the band is redshifted by 20 cm–1 in complex 6, where this bond is 0.2 Å longer than in other compounds. It is shown that parameters ν(Sn–O), a(117, 119Sn) and bond lengths d(Sn–O), d(Sn–N), and d(Sn–C) in the complexes depend on four (inductive, resonance, polarization, and steric) effects of tin-bonded substituents.

The article is concerned with the influence of resonance donor substituents R D on the dipole moments μ of molecules 1,4-R D C 6 H 4 R A containing resonance acceptor groups R A (CF 3 , CN, COCH 3 , NO 2 or COH) and grouped in five reaction (indicator) series. Generally, the μ values depend on the inductive, resonance, and polarizability effects of the substituents R D . Strengthening of the resonance acceptor properties of the R A groups leads to weaker conjugation between the substituents R D and the π-system.

•The dipole moments μ of organometallic complexes have been analyzed.•The μ values depend on the polarizability effect of substituents X.•The contribution of the polarizability effect ranges up to 50%.

The thermal decomposition of cluster Nd3I5(S2)(S2N2)(THF)10 (I) at 50–400°C affords a mixture of products among which tetrahydrofuran (THF), sulfur, diiodine, HI, H2S, CS2, S3N6, S3N5, MeI, thiophene, tetrahydrothiophene, diiodobutane, iodobutene, and NdI3 are identified. The treatment of Ln3I5(S2)(S2N2)(THF)10 (Ln = Nd (I), Dy (II)) with phenanthroline (Phen) in THF at room temperature results in the partial substitution of ТНF to form new complexes Ln3I5(S2)(S2N2)(THF)4(Phen)3. The dissolution of compound I in pyridine gives a pyridine (Py) complex Ln3I5(S2)(S2N2)(THF)3(Py)7. The dissolution of compounds I and II in acetonitrile at 20°C is accompanied by the fast rearrangement and fragmentation of the complexes to form LnI3(MeCN)6, [LnI(S2)(MeCN)], and [LnI(S2N2)(MeCN)]. Complex I in THF does not react with white phosphorus, carbon monoxide, fullerene C60, and chromium hexacarbonyl.