S. P. Kuleshov

Dehydration of LnCl3·6H2O (Ln=Tb, Nd, Dy) in the reaction with i-Bu3Al, Et3Al, Et2AlCl, EtAlCl2 and formation of the complexes LnCl3·3(BuO)3PO

Abstract The dehydration of toluene insoluble salts TbCl 3 ·6H 2 O ( 1 ), DyCl 3 ·6H 2 O ( 2 ) and NdCl 3 ·6H 2 O ( 3 ) in their reaction with organoaluminum compounds (R n AlX 3− n ): i -Bu 3 Al, Et 3 Al, Et 2 AlCl, EtAlCl 2 and the influence of (BuO) 3 PO (TBP) on the process were studied. In the reaction of R n AlX 3− n with the water of crystallization of salts 1 – 3 , aluminoxanes and the following gases are formed: i -BuH for i -Bu 3 Al, EtH for Et 3 Al, EtH and HCl for Et 2 AlCl and EtAlCl 2 as a result of the attack on the AlC or AlCl bond independent of the presence of TBP. In the absence of TBP the salts 1 – 3 are dehydrated by R n AlX 3− n to give insoluble products LnCl 3 ·0.5H 2 O·0.5(R 2 Al) 2 O, where R is alkyl for i -Bu 3 Al and Et 3 Al, or R is alkyl and Cl for Et 2 AlCl. The reaction of R n AlX 3− n with 1 – 3 in the mixture of toluene–TBP at the ratio TBP/Ln≥12:1 results in the complete removal of water from LnCl 3 ·6H 2 O and leads to the formation of homogeneous solutions, containing aluminoxanes and LnCl 3 ·3TBP complexes. Homogeneous solutions, obtained after interaction in the system NdCl 3 ·6H 2 O+TBP+PhMe+R 3 Al were then activated with either i -Bu 3 Al or ( i -Bu 2 Al) 2 O and used as catalysts for polymerization of butadiene. All the catalysts were highly active for polymerization of butadiene, and produced a low-molecular polybutadiene.

On the mechanism of the chemiluminescent condensation of aniline with butyraldehyde catalyzed by LnCl3 · 6H2O

The mechanism of the chemiluminescent condensation of aniline with butyraldehyde into 3-ethyl-2-propylquinoline catalyzed by LnCl3 · 6H2O (Ln = Tb, Ho) is reported. A likely scheme of the catalytic condensation of aniline with butyraldehyde has been developed by simulation of separate steps of the reaction using chemiluminescence and photoluminescence methods and quantum-chemical calculations of the heats of these steps.

Effect of crystallization water and nature of an aluminum alkyl on the reduction of Eu3+ to Eu2+ in interaction of EuCl3 · 6H2O with Bu3i Al and Et3Al

Volumetric and photoluminescence analytical techniques were employed to study the effect of crystallization water and nature of an aluminum alkyl on the reduction of Eu3+ to Eu2+ in a heterophase interaction of EuCl3 · 6H2O in toluene with Bu3i Al and Et3Al.

Reactions of lanthanide acetylacetonates with triethylaluminum

The reactions of lanthanide acetylacetonates Ln(acac)3 · H2O (Ln = Nd, Tb, Ho, Lu) with Et3Al in toluene were studied by spectral methods (photoluminescence; taumetry; NMR, IR, and UV-vis spectroscopy) using GLC, volumetry, and chemical analysis.

Chemiluminescence during thermolysis of the (Ph3COOCPh3)n—Ph3C· peroxide containing captured triphenylmethyl radical

Chemiluminescence (CL) in the thermolysis of (Ph3COOCPh3)n—Ph3C· containing the triphenylmethyl radical captured during the synthesis of Gombergs peroxide was found. Two CL emitters were identified: the triplet state of benzophenone (3Ph2CO*) and Ph3C·*. Ph3C·* is formed due to the energy transfer from the excited 3Ph2CO* generated in the disproportion of thermolysis intermediates, Ph3CO· radicals. This Ph3C·* luminescence is the first example of CL activation by an organic radical. Chemiluminescence during the thermolysis of Ph3COOCPh3 containing no Ph3C· is resulted from the emission of one emitter, 3Ph2CO*. The solid-phase CL was found during the oxidation of Ph3C· with dioxygen after the destruction of the crystalline lattice as a result of the thermolysis of the (Ph3COOCPh3)n—Ph3C· peroxide.

Chemiluminescence of Ru(bpy)3 2+* in the reaction of electron transfer from Ph3CNa to Ru(bpy)3 3+ in a solution

Conditions for the generation of the Ru(bpy)33+ complex in organic solvents (Me3CN or MeNO2) in the presence of small amounts of H2SO4 were found. Chemiluminescence was observed in the reaction of Ru(bpy)33+ with Ph3Na in a THF-MeCN mixture. The chemiluminescence emitter was identified as Ru(bpy)32+*. This emitter forms in the excited state in the elementary reaction of electron transfer from the Ph3C− anion to Ru(bpy)33+.

Chemiluminescence testing of solutions to detect organometallic peroxides during oxidation of organometallic compounds by oxygen

Conclusions1.The possibility of detecting organometallic peroxides without decreasing the temperature and hydrolysis of the reaction solution during oxidation of organometallic compounds with oxygen based on the kinetic maxima of the intensity of chemiluminescence was demonstrated.2.The formation of organometallic peroxides was detected during oxidation of organic derivatives of uranium and lanthanides with oxygen.3.The stage of formation of an organometallic peroxide during oxidation of organometallic compounds with oxygen takes place more rapidly than the reactions of its subsequent consumption.

Reaction of 3-(alken-1-yl)-4,5-dihydro-3H-pyrazoles with sodium nitrite in acetic acid

Abstract3-Vinyl-4,5-dihydro-3H-pyrazole reacted with sodium nitrite in acetic acid to give 3-vinyl-1-nitroso-4,5-dihydro-1H-pyrazole, whereas 3-isopropenyl-4,5-dihydro-3H-pyrazole under analogous conditions was unexpectedly converted into a nitro derivative, 3-(1-methyl-2-nitrovinyl)-4,5-dihydro-1H-pyrazole.

Interaction of terbium acetylacetonate with diethylaluminum chloride

The interaction of terbium acetylacetonate Tb(acac)3 · H2O with Et2AlCl in toluene was studied by spectroscopic techniques (photoluminescence, IR, and UV-visible spectroscopy) with the use of GLC, volumetric, and chemical analysis.

Red and green chemiluminescence of Na, Mg, and lanthanide triphenylmethyl derivatives during oxidation by dioxygen and cerium(IV)

Chemiluminescence (CL) of triphenylmethyl organometallics (TPM), Ph3CNa, Ph3CMgCl, and Ph3CLnCl2 (Ln=Cd, Eu, and Dy), in THF and toluene during oxidation by O2 and the (NH4)2Ce(NO3)6 complex was found. The first CL is caused by the luminescence of two emitters: (Ph3C)*, emitting in the green spectral region (λmax=524, 550 nm), and an unstable product of substitution of the hydrogen atom in the phenyl ring of the Ph3C radical, emitting in the red region (λmax=580±20 nm). The emitter of the second CL, Ph3C.*, is generated in the elementary electron transfer from the Ph3C− anion to CeIV, reducing the latter to CeIII.