Matrix IR-spectroscopic and quantum-chemical study of difluorostannylene complexation with dinitrogen

Complexes of difluorostannylene with dinitrogen of composition 1∶1 and 1∶2 were stabilized in Ar matrix (12 K) and characterized by IR spectra. The bands at 588, 565, and 583, 557 cm⁻¹, respectively, were assigned to these complexes. Potential energy surfaces of the systems SnF₂+N₂ and SnF₂+2N₂ were studied by theab initio MP2/3-21G(d2)//HF/3-21G(d2) method using the basis set including polarization functions at Sn, F, and N atoms. Equilibrium structures of the complexes haveC _s andC _2v symmetry and correspond to coordination of lone electron pairs of nitrogen molecules with vacant p-AO of the carbenic center. The calculated complexation energies are equal to 4.6 and 8.9 kcal mol⁻¹, respectively. Based on results of quantum-chemical calculations an interpretation of the IR spectra of the complexes was given and it was shown that cycloaddition of SnF₂ to a triple N≡N bond with formation ofcyclo-SnF₂N₂ is energetically unfavorable. The absorption band belonging to SiF₄·N₂ complex in Ar matrix was detected and assigned. Dedicated to the memory of Academician M. E. Vol'pin timed to his 75th birthday. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1087–1093, June, 1998.     

IR spectroscopic study of the interaction between trimethylgallium and arsine in the liquid phase

The formation of a donor-acceptor complex Me₃Ga · AsH₃ in a solution in liquid krypton at 130 K and in a binary liquid solution of those substances at 263 K was established by IR spectroscopy. In the latter case, Me₃Ga and AsH₃ react at an appreciable rate to form an amorphous product of composition Me_3-x ,GaAsH_3-x .Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2259–2262, September, 1996.     

Contrasting behavior in azide pyrolyses: an investigation of the thermal decompositions of methyl azidoformate, ethyl azidoformate and 2-azido-N, N-dimethylacetamide by ultraviolet photoelectron spectroscopy and matrix isolation infrared spectroscopy

The thermal decompositions of methyl azidoformate (N3COOMe), ethyl azidoformate (N3COOEt) and 2-azido-N,N-dimethylacetamide (N3CH2CONMe2) have been studied by matrix isolation infrared spectroscopy and real-time ultraviolet photoelectron spectroscopy. N2 appears as an initial pyrolysis product in all systems, and the principal interest lies in the fate of the accompanying organic fragment. For methyl azidoformate, four accompanying products were observed: HNCO, H2CO, CH2NH and CO2, and these are believed to arise as a result of two competing decomposition routes of a four-membered cyclic intermediate. Ethyl azidoformate pyrolysis yields four corresponding products: HNCO, MeCHO, MeCHNH and CO2, together with the five-membered-ring compound 2-oxazolidone. In contrast, the initial pyrolysis of 2-azido-N,N-dimethyl acetamide, yields the novel imine intermediate Me2NCOCH=NH, which subsequently decomposes into dimethyl formamide (HCONMe2), CO, Me2NH and HCN. This intermediate was detected by matrix isolation IR spectroscopy, and its identity confirmed both by a molecular orbital calculation of its IR spectrum, and by the temperature dependence and distribution of products in the PES and IR studies. Mechanisms are proposed for the formation and decomposition of all the products observed in these three systems, based on the experimental evidence and the results of supporting molecular orbital calculations.     

Experimental and theoretical study of the reaction of difluorostannylene with methyl chloride. The first direct IR spectroscopic detection of a complex between a carbene analog and an alkyl halide in low temperature inert matrix

Complex between a carbene analog (SnF₂) and organo halide (CH₃Cl) was stabilized by a low-temperature (Ar, 12 K) matrix isolation technique and characterized by IR spectroscopy for the first time. The bands at 567 and 543 cm^–1 were assigned to this complex. The potential energy surface of the system SnF₂ + CH₃CI was studied byab initio MP2/ 3-21G(d)//HF/3-21G(d) and semiempirical PM3 methods. Calculations shown that the reaction between SnF₂ and CH₃C1 results in the formation of a donor-acceptor complex. The calculated energy of the complex formation is 14.2 kcal mol^–1 (ab initio) and 15.7 kcal mol^–1 (PM3). Quantum-chemical calculations were used to interpret the IR spectrum of the complex. Insertion of SnF₂ into the C-Cl bond with formation of CH₃SnF₂Cl is an energetically favored process but it requires surpassing of a high energetic barrier and does not occur under the experimental conditions. A complex of CH₃CI with H₂O codeposited in argon matrix was detected by IR spectroscopy for the first time.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1121–1128, May, 1996.     

Conflicting Observations Resolved by a Far IR and UV/Vis Study of the NO3 Radical

Codeposition of NO and O ₂ diluted in Ne at 6 K yield a ON???OO complex that exhibit strong UV absorption. This complex is converted into NO₃ radicals by UV irradiation, and is regenerated by radiation of visible light (see spectra).

     

Generation and IR spectroscopic study of benzyl radical

The benzyl radical C₆H₅CH₂ has been obtained by gas phase pyrolysis of two different precursors, benzyl bromide and dibenzyl, and studied in an argon matrix at 12 K by IR spectroscopy. Similarly, the deuterosubstituted benzyl radicals, C₆H₅CD₂ and C₆D₅CH₂, have been investigated. The assignment of the IR bands of the benzyl radical and its deuteroanalogs to fundamental modes and a calculation of the valence force field have been performed. The obtained data give evidence of sp² hybridization of the methylene carbon atom and delocalization of the electron density between the ring and the CH₂ group, and are in good agreement with the planar structure of the radical.These results were presented for the first time in O. M. Nefedov's plenary lecture at X IUPAC Conference on Physical Organic Chemistry (Haifa, Israel, August 1990).Deceased July, 1986.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1499–1502, August, 1993.     

Noncovalent complexes between dimethyl ether and formic acid--an ab initio and matrix isolation study.

The complexes formed by noncovalent interactions between formic acid and dimethyl ether are investigated by ab initio methods and characterized by matrix isolation spectroscopy. Six complexes with binding energies between -2.26 and -7.97 kcal mol(-1) (MP2/cc-pVTZ+zero point vibrational energy+basis set superposition erros) are identified. The two strongest bound complexes are, within a range of 0.3 kcal mol(-1), isoenergetic. The binding in these six dimers can be described in terms of OH...O, C=O...H, C-O...H and CH...O interactions. Matrix isolation spectroscopy allowed to characterize the two strongest bound complexes by their infrared spectra.     

IR spectroscopic study of allylperoxy radical and products of its phototransformations in the Ar matrix

Matrix IR spectra of an allylperoxy radical (1) obtained by co-condensation of allyl radicals and molecular oxygen into an argon matrix at 12 K have been studied. The bands observed in the matrix IR spectrum are assigned to normal vibrations on the basis of ab initio calculations of radical1 and its isotope-substituted analog CA 18_{O 2} (1a). The band at I128.6 cm^–1 is assigned to the stretching vibration of the 0-0 bond. The products of photodecomposition of radical1 under UV irradiation ( > 248 nm) have been studied. A vinylacyl radical (2) with a characteristic high vibrational v(C=0) frequency of 1823.I cm -1 has been observed among the products of photolysis of1. According to the data of quantum chemical calculations, some delocalization of a free electron between an oxygen atom and two C atoms is observed in radical 2.Preliminary results were presented at the XII International Conference on Physical Organic Chemistry (Padova, Italy) in 1994.¹⁵ Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. I, pp. 109–116, January, I996.     

Complexes of carbene analogs with Lewis bases: matrix IR spectroscopy and quantum-chemical studies

The results of studies on complexes of carbene analogs ER₂ (E = Si, Ge, Sn, Pb) with Lewis bases by matrix IR spectroscopy and quantum chemistry methods are considered. Trends in changes in the spectral characteristics, structures, and stability of the complexes are outlined.     

High-vacuum pyrolysis of 1,1,1-trifluoro-2-bromo-2-chloroethane. IR spectrum of 1,1,1-trifluoro-2-chloroethyl radical in an argon matrix

The products of high-vacuum pyrolysis of 1,1,1-trifluoro-2-bromo-2-chloroethane were studied by matrix IR spectroscopy. The decomposition of 1,1,1-trifluoro-2-bromo-2-chloroethane was shown to occur predominantlyvia two directions: to form the 1,1,1-trifluoro-2-chloroethyl radical and trifluoromethylcarbene isomerizing to trifluoroethylene. The CF₃CHCl radical has been detected in the matrix for the first time. The bands observed in the IR spectrum were calculated by the quantum-chemical B3LYP/6-311 G(d,p) method and assigned to normal vibrations of the radical. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2085–2088, October, 1998.     

Intermediates of photolysis of 1,3,2,4-benzodithiadiazines studied by matrix isolation spectroscopy and quantum chemistry

Photolysis of 12-electron, formally antiaromatic, 1,3,2,4-benzodithiadiazine (1a) and its tetrafluoro-substituted derivative (1b) was studied in glassy matrices at 77 K and in an argon matrix at 14 K by UV, IR, and ESR spectroscopy. In these matrices, a diamagnetic species (3a,b) is formed as a persistent species. It is product of the intramolecular transformations of heterocycles 1a,b and the precursor of 1,2,3-benzodithiazolyl radicals (2a,b). The nitrenoid structure, intermediate between the structures of singlet 1,2,3-benzodithiazol-2-ylnitrene RS—N: and the corresponding thiazyl RSN, was ascribed to intermediate 3a,b in agreement with the data of IR spectroscopy.     

Characterization of fungal degraded lime wood by FT-IR and 2D IR correlation spectroscopy

The action of soft-rot fungus Chaetomium globosum has been studied. The decayed lime wood samples were observed for different periods of exposure. The degree of decay was determined by weight loss which was of 50.4% after 133 days. The samples were analyzed by FT-IR and 2D IR correlation spectroscopy.The intensity bands assigned to different vibrations from cellulose and hemicelluloses show a decrease, while the intensities of the bands assigned to C–O vibrations due to the formation of oxidized structures increase. At the same time, the intensity of the band assigned to C–O in metoxyl groups from lignin shows a decrease with increasing exposure time. The differences between reference and decayed wood spectra were examined in detail using 2D correlation spectroscopy and the second derivative analysis for two exposure time periods — of 0–70 days and 70–133 days. The formation of reactive species due to oxidation reactions induced by enzymes and the demethoxylation of the lignin structure was evidenced.     

Acidity of heteropoly acids with various structures and compositions studied by IR spectroscopy of the pyridinium salts

The acidity on the proton affinity scale was determined by IR spectroscopy of the pyridinium salts for nineteen heteropoly acids of nine structural types (including two with the previously unknown structure) and one isopoly acid. All heteropoly acids exhibited a high acidity at the level of CF₃SO₃H and HClO₄. H₃PW₁₂O₄₀ was the strongest acid.     

Thermal decomposition of allantoin as probed by matrix isolation FTIR spectroscopy

The optimized geometries, energies of the possible conformers of allantoin (2,5-dioxo-4-imidazolidinyl urea, the diureide of glyoxylic acid) as well as the barriers for conformational interconversion have been calculated using the density functional theory [DFT(B3LYP)/6-311++G(d,p)] method. The calculations predicted the existence of four conformers (gC, tT, g′C, and g′T; where the first and second symbols in the name of the conformers designate the conformation around the exocyclic NHC-NHCO and CNH-CO axes, respectively), with the gC form contributing to more than 98% of the population in gas phase at room temperature. This conformer is different from that corresponding to the monomeric unit found in crystalline RS-allantoin (g′C; Mootz, D. Acta Crystallogr.1965, 19, 726), stressing the importance of intermolecular H-bonding in determining the structure of the crystal. Upon sublimation under vacuum (10⁻⁶ mbar), the compound was found to undergo extensive decomposition to urea, isocyanic acid, NH₃, and carbon. The identification of the decomposition products was made by using matrix isolation infrared spectroscopy. In consonance with the theoretical predictions, the allantoin molecules surviving thermal decomposition were found to undergo conformational isomerization and be present in the cryogenic argon matrix in both the gC and g′C conformations. The solid state room temperature infrared spectrum of allantoin was also investigated and assigned.     

Low-pressure pyrolysis of tBu2SO: synthesis and IR spectroscopic detection of HSOH

Sulfenic acid (HSOH, 1 ) has been synthesized in the gas‐phase by low‐pressure high‐temperature (1150 °C) pyrolysis of di‐tert‐butyl sulfoxide (tBu₂SO, 2 ) and characterized by means of matrix isolation and gas‐phase IR spectroscopy. High‐level coupled‐cluster (CC) calculations (CCSD(T)/cc‐pVTZ and CCSD(T)/cc‐pVQZ) support the first identification of the gas‐phase IR spectrum of 1 and enable its spectral characterization. Five of the six vibrational fundamentals of matrix‐isolated 1 have been assigned, and its rotational‐resolved gas‐phase IR spectrum provides additional information on the O–H and S–H stretching fundamentals. Investigations of the pyrolysis reaction by mass spectrometry, matrix isolation, and gas‐phase FT‐IR spectroscopy reveal that, up to 500 °C, 2 decomposes selectively into tert‐butylsulfenic acid, (tBuSOH, 3 ), and 2‐methylpropene. The formation of the isomeric sulfoxide (tBu(H)SO, 3 a ) has been excluded. Transient 3 has been characterized by a comprehensive matrix and gas‐phase vibrational IR study guided by the predicted vibrational spectrum calculated at the density functional theory (DFT) level (B3LYP/6‐311+G(2d,p)). At higher temperatures, the intramolecular decomposition of 3 , monitored by matrix IR spectroscopy, yields short‐lived 1 along with 2‐methylpropene, but also H₂O, and most probably sulfur atoms. In addition, HSSOH ( 6 ), H₂, and S₂O are found among the final pyrolysis products observed at 1150 °C in the gas phase owing to competing intra‐ and intermolecular decomposition routes of 3 . The decomposition routes of the starting compound 2 and of the primary intermediate 3 are discussed on the basis of experimental results and a computational study performed at the B3LYP/6‐311G* and second‐order Møller–Plesset (MP2/6‐311G* and RI‐MP2/QZVPP) levels of theory.     

Distribution of the strength of acid sites in mildly steamed HZSM-5 studied by IR spectroscopy

Steaming resulted in modification of the distribution of acid strength of OH groups. The contribution of less acidic sites increased and new, very strongly acidic hydroxyls characterized by IR band at 3590 cm^-1 appeared.     

Formation of quinoid fragments in vacuum-deposited poly-para-phenylene films: IR spectroscopy evidence

The structure of vacuum-deposited poly-para-phenylene (PPP) films prepared from a high-molecular-weight PPP powder has been investigated by IR spectroscopy. It has been demonstrated that in IR spectra of PPP films exhibiting intense luminescence an extremely strong band at 1375 cm⁻¹ is observed, which is not typical for currently known PPP modifications. Based on the IR spectral data, the model of formation of a PPP chain with quinoid fragments in the ground electronic state is proposed. The structure of defects that inevitably spring up during the benzenoid–quinoid transition is discussed. High intensity of the band at 1375 cm⁻¹ is associated with the change in the order of the “defect” C C bond between adjacent quinoid and benzenoid units. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1043–1052, 1998     

Study of intermolecular interactions and complex formation of aminofurazans by IR spectroscopy

The IR spectra of 3-amino-4-nitrofurazan (1) and 4-amino-4-nitroazoxyfurazan (2) in the crystalline state and in solutions in CH{in2}Cl{in2}, CCl{in4}, and MeCN have been studied. It was shown that both compounds exist in the solid state as self-associates, which are destroyed on dissolution in an organic solvent. Compouns1 and2 form associate complexes with MeCN, the energies of formation of which are –5 and –3 kcal mol{su–1}, respectively.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2242–2246, December, 1994.     

Thermal oxidation of poly(1-trimethylsilylprop-1-yne) studied by IR spectroscopy

Thermal oxidation of poly(1-trimethylsilylprop-1-yne) was studied by IR spectroscopy in the 20—245 °C temperature interval. In the 20—160 °C temperature range, the reaction proceeds predominantly at the C—Me group as revealed by the decrease in the intensity of the bands of the methyl group bound to the C atom and the appearance of the bands of the hydroperoxide and methylene groups. The decomposition of hydroperoxides produces aldehydes and ethers. At 160—200 °C, oxidation occurs via two routes: at the C—Me and C=C groups, while the Me₃Si group remains unchanged. At 230—240 °C, the rate of the reaction occurring at the C=C bond is higher than the rates of the processes involving the MeC and Me₃Si groups. The relative content of the structural units was calculated for the samples oxidized at different temperatures. Plausible mechanisms of thermal oxidation of poly(1-trimethylsilylprop-1-yne) were considered on the basis of the data obtained.