The heteromolecular insertion of carbon dioxide in combination with heterocumulenes, iso(thio)cyanates or N,N′ -dicyclohexylcarbodiimide, into rhenium–alkoxy group bond was accomplished for the first time in relation to reactivity of rhenium oxoalkoxides. The ease of combined insertion of iso(thio)cyanate and carbon dioxide into Re–O(Me) bond is determined by the nature of the heterocumulene organic group. Indeed, if ethyl iso(thio)cyanate is used in the reaction, the insertion is reversible, whereas the reaction with PhNCS (unlike PhNCO) together with carbon dioxide leads to complete insertion into two Re–O(R) bonds to give the insertion product (OMe) 10 O 6 Re 4 [OC(O){N(Ph)C(S)} 2 -OMe] 2 . In similar reactions carried out with N,N′ -dicyclohexylcarbodiimide, a dependence of the number of bonds participating in the inner-sphere condensation of the inserted moieties on the duration of the experiment was found for the first time. An increase in the time of synthesis from 3 to 5 h results in insertion involving six rather than three bonds, the heteromolecular insertion products being (OMe),O 6 Re 4 {OC(O)[(Hex)N=C=N(Hex)] 2 } 3 and (OMe) 6 O 6 Re 4 {OC(O)[(Hex)N=C=N(Hex)] 2 } 6 , respectively.

It has been proposed to conduct the synthesis of cerium(III) orthophosphates by reacting cerium(IV) compounds with hydrogen peroxide in the presence of concentrated orthophosphoric acid at ambient temperature. It has been shown that the reaction of H 2 O 2 with CeO 2 suspensions in H 3 PO 4 medium produces CePO 4 · x H 2 O (rhabdophane structure), while that with CeO 2 solutions in concentrated H 3 PO 4 results in CePO 4 (monazite structure).

Реакцией синтезированных в присутствии глутаминовой кислоты гидроксиапатита с парами H2O2 при 10°C и брушита CaHPO4.2H2O с 90%-ным раствором H2O2 при 0°C получены соответствующие пероксосольваты с содержанием пероксида водорода до 18%. Изучена морфология (РЭМ) пероксосоединений и продуктов их распада при 170–960°C. Рассмотрены факторы, влияющие на размер частиц.

Reacting hydroxyapatite with H 2 O 2 vapor at 10°C and brushite CaHPO 4 · 2H 2 O with 90% H 2 O 2 solution at 0°C (the hydroxyapatite and brushite were both prepared in the presence of glutamic acid) yielded the relevant peroxo solvates containing up to 18% hydrogen peroxide. The peroxo compounds and their degradation products obtained at 170–960°C were morphologically studied (using SEM). The factors influencing particle sizes are considered.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Reactions of the higher molybdenum and tungsten chlorides with phenyl isothiocyanate or with N , N ′-dicyclohexylcarbodiimide and carbon dioxide in dichloroethane are the first to demonstrate the possibility of insertion of carbon dioxide in combination with other heterocumulenes into transition metal-halogen bonds. IR spectroscopy and elemental analysis data show that the reactions result in the attachment of the ligands at the same metal-chlorine bond and the formation of heteromolecular insertion products with the compositions [ MoOCl_3 {N( Ph)C( S )}_2 Nc( Me)Cl] and MCl_x {OC( O )[ ( Hex)NCN( Hex)]_2 }Cl, where x = 4 and 5 for the Mo and W derivatives, respectively.

На примере реакций высших хлоридов молибдена и вольфрама с фенилизотиоцианатом или с N,N1-дигексилкарбодиимидом и диоксидом углерода в среде дихлорэтана впервые выявлена возможность внедрения диоксида углерода в сочетании с другими гетерокумуленами по связи переходный металл–галоген. Совокупность данных ИК-спектроскопии и элементного анализа указывает на то, что результатом реакций является совместное присоединение лигандов по одной и той же связи металл–хлор с образованием продуктов гетеромолекулярого внедрения составов

Reactions of rhenium pentachloride with ethyl isocyanate in dichloroethane and acetonitrile are the first to demonstrate the feasibility of inserting organic isocyanates and nitriles into a rhenium-halogen bond. IR spectroscopy and elemental analysis data show that the addition of one to three ethyl isocyanate molecules in dichloroethane yields ReCl4[N(Et)C(O) n ]Cl with n = 1−3, depending on the relationship between the reactants. The reaction in acetonitrile yields a heteromolecular insertion product containing a chain of two isocyanate groups and one nitrile group attached to the same rhenium-chlorine bond: ReCl4[{N(Et)C(O)}2N=C(Me)Cl]. When EtNCS is used instead of EtNCO, the reaction is reversible.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Preparations of peroxotalc containing up to 6% Oact have been synthesized and studied by vibrational spectroscopy (IR, Raman), X-ray diffraction, and TGA. The stability of the compounds on storage and heating under iso- and polythermal conditions has been studied. The presence of peroxo groups was confirmed spectroscopically.

Simple strontium peroxodisulfate SrS 2 O 8 · 4H 2 O was synthesized by the reaction of solid Sr(OH) 2 · 8H 2 O taken in 30% excess with an aqueous solution of (NH 4 ) 2 S 2 O 8 ; simple magnesium peroxodisulfate MgS 2 O 8 · 6H 2 O was synthesized by the reaction of an aqueous solution of BaS 2 O 8 with a stoichiometric amount of MgSO 4 · 7H 2 O. Persulfate ammine complexes [M(NH 3 ) 4 ]S 2 O 8 (M = Zn, Cu) were prepared in concentrated aqueous ammonia from [Zn(NH 3 ) 4 ](OH) 2 , [Cu(NH 3 ) 4 ](OH) 2 , and an ammoniac solution of (NH 4 ) 2 S 2 O 8 . The compounds were characterized by X-ray powder diffraction (pRSA) and vibrational (IR and Raman) spectroscopy. Their stability was studied during storage and in DTA experiments. The [Zn(NH 3 ) 4 ]S 2 O 8 structure was solved. Its crystals are orthorhombic, a = 10.5512(8) Å, b = 12.8039(12) Å, c = 8.0448(5) Å, V = 1086(15) Å 3 , Z = 4, space group Pna 2 1 . The compound is built of [Zn(NH 3 ) 4 ] 2+ complex cations and S 2 O 8 2− persulfate anions. In a cation, Zn-N bond lengths are within 2.04(2)–2.056(14) Å. In an anion, the lengths of S(1)–O(4), S(2)–O(5), and O(4)–O(5) bridging bonds are, respectively, 1.676(14), 1.672(16), and 1.465(16) Å; the other S–O bond lengths are within 1.409(14)–1.443(12) Å; the S(1)O(4)O(5)S(2) torsion angle is 140.8(7)°.

Calcium peroxosilicates CaO·nSiO2·xH2O·yH2O2 (n = 1, 2) were synthesized by three methods: (1) the reaction of CaSiO3·nH2O (∼7% CaSiO3 suspension in water) with 50.7, 73.4, and 92% H2O2 at 0–5°C produced compositions CaSiO3·6H2O·2H2O2, CaSiO3·2H2O·4H2O2, and CaSiO3·3H2O·8H2O2, respectively; (2) the reaction of CaSiO3·17H2O with 50.7 and 73.4% H2O2 at 0–5°C produced the solvate CaO·2SiO2·4H2O·0.15H2O2; and (3) the reaction of CaSiO3·3H2O with H2O2 vapor at 5°C in the absence of anhydrone produced the solvate CaSiO3·3.5H2O·0.5H2O2. The products were characterized by X-ray powder diffraction, thermogravimetry, and IR spectroscopy.

Dynamical character of thermotropic liquid crystals - p-n-alkyloxy-p'-cyanobiphenyls structure was investigated by infrared spectroscopy method.Quantum - chemical calculations of infrared spectrum, geometrical and electronic cyanobiphenyls molecules structure for different angle a between phenyl rings planes volumes were operated by B3LYP/6-31+G** method. Shown, that twist-conformation with angle alpha approximate to 37 degrees is the most stable molecule conformation. In accord with the calculations the increase of angle leads to the 5 sm(-1) increase in - CN-group alpha-frequency fluctuations, but infrared region intensity decreases two times. Aliphatic chain lengthening does not bring any marked difference of molecule central part geometric structure, and calculated - CN-group frequency fluctuations. Shown, that cyanobiphenyl molecules conformation conversions, particularly in the alkyloxy-radicals part, play a determinate role in liquid crystals mesogens.

Anhydrous lanthanum nitrate and its complexes with one and two ethylenediamine molecules are calculated by the ab initio B3LYP/LANL2DZ quantum-chemical method. An ethylenediamine molecule is shown to coordinate preferentially through one amino group, and a hydrogen bond is formed between the coordinated amino and nitrato groups. An ethylenediamine complex of lanthanum nitrate is synthesized, and its composition and thermal stability are determined. The IR spectra of the ethylenediamine complex of lanthanum nitrate confirm the presence of the intramolecular hydrogen bond in this complex.

Complexes with the compositions [Fe(Phen)3]2(S2O8)3 · 2H2O, [Co(Phen)3]2(S2O8)3 · 8H2O, Co(Phen)2S2O8 · 3H2O, and [Ni(Phen)2(H2O)2]S2O8 were synthesized and studied by spectroscopic, X-ray powder diffraction, and TG methods.

The donor ability of quinoline, benzoquinoline, and phenanthroline is measured based on the shift of the O-H stretching band of phenol in highly dilute solutions in CCl4 at a 1: 1 molar ratio of the components. The results obtained are compared with analogous values for aliphatic amines and diamines. The conclusion is drawn on the influence of the aromatic rings and the second nitrogen atom in the ligand molecule on the donor ability of a nitrogen-containing neutral molecule during complexation with lanthanide ions.

New palladium(I) carbonyl carboxylate complexes of composition [Pd(CO)(OCOR)] n , where R is a linear or branched alkyl fragment C n H 2 n + 1 (n = 3, 4, or 5), were synthesized. The presence of bulky alkyl fragments inthe carboxylate ligand increases the nuclearity of the cluster compared to that of the starting palladium(I) carbonyl acetate of composition Pd 4 (CO) 4 (OAc) 4 (I) due, apparently, to steric hindrance. The replacement of acetate groups with pivalate groups [OCOCMe 3 ] affords the hexanuclear cluster Pd 6 (CO) 5 (OCOCMe 3 ) 6 (II). The structure of cluster II was established by X-ray diffraction analysis. The crystals of II (C 4 2 H 6 0 O 1 8 Pd 6 , M = 1491.30) belong to the orthorhombic system, space group P2 1 2 1 2 1 , a = 10.758(2) A, b = 26.291(5) A, c = 19.067(3) A, V = 5393(2) A 3 , Z = 4. The cyclic metal core of cluster II is planar (within 0.12 A). Alternating pairs of pivalate and carbonyl ligands are coordinated on opposite sides of the metal core.