Inversion and inversion-rotation spectrum of 14NH3 in the ν2 excited state

Using the vibration-inversion-rotation Hamiltonian for ammonia [V. ?pirko, J. M. R. Stone, and D. Papou?ek, J. Mol. Spectrosc.60, 159–178 (1976)], a modified theory is worked out for the Δk = ±3n interactions between the inversion-rotation energy levels of NH₃ which takes into account the large amplitude inversion motion. Eighty frequencies of inversion and inversion-rotation transitions and two perturbation-allowed transitions in the ν₂ state of ¹⁴NH₃ are measured in the far-infrared region around 1 THz (≈33 cm^?1), mostly with the microwave accuracy, by the radiofrequency spectrometer with acoustic detector. By a least-squares fit of these data and the data of the infrared-microwave two-photon and infrared heterodyne measurements of the ν₂ band, a set of molecular constants for the ν₂ state of ¹⁴NH₃ is obtained which reproduces the submillimeterwave data with the accuracy of the experiment.     

Study of microwave pressure lineshifts: Dynamic and isotopic dependences

The study of pressure lineshifts and line broadenings initiated earlier (J. Mol. Spectrosc.94, 264–282 (1982)) is extended to some other perturbing gases and to isotopic species. New dependences of the lineshifts on the molecular parameters are found. One of them is the dependence, as well as the proportionality of the lineshift to the line frequency found before is explained in terms of a “dynamic Stark effect” model. The dependence of the lineshifts on the isotopic composition of the absorbing molecule is also reported. One of the main results of the study is the demonstration of higher sensitivity of lineshifts to the characteristics of molecular interactions as compared to the corresponding line broadening.     

Optically active diethyl ester of α-aminobenzylphosphonic acid

Conclusions The (–)-diethyl ester of-aminobenzylphosphonic acid was obtained.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 955–956, April, 1973.     

Low-Temperature Anti-Stokes Luminescence in Zn1-xMgxSe Mixed Crystals

Investigations of photoluminescence and Raman scattering in the ternary Zn_1-xMg_xSe compounds at 4.2 K were performed both in the Stokes and anti-Stokes regions using cw laser excitation with various wavelengths within the transparency band of the crystals. The anti-Stokes luminescence was observed for the first time in the ternary Zn_1-xMg_xSe compounds. We have found variations in the shape and position of the Stokes and anti-Stokes luminescence bands with an increase in the band gap energy, which depends on magnesium content. We assume that the anti-Stokes emission is generated by two-step excitation via deep-level centers. It is shown that the low-temperature anti-Stokes photoluminescence can probe the spatial distribution profiles of impurities in the bulk of crystals.     

Palladium Complexes as Catalysts for the Synthesis of Functional Polymers Based on Carbon Monoxide

A review of the history and present state of the use of palladium complexes in the synthesis of alternating CO copolymers with different monomers (mainly ethylene, propylene, and styrene) is presented. The effect of mono- and bidentate phosphine ligands, the nature of reaction medium and acid on the rate of the CO copolymerization with ethylene, and the effect of different bidentate PP, PN, and NN ligands on the structure and properties of chiral CO–propylene and CO-styrene copolymers are considered.     

Spirocyclopropanated bicyclopropylidenes: straightforward preparation, physical properites, and chemical transformations

Perspirocyclopropanated bicyclopropylidene (6) was prepared in three steps from 7-cyclopropylidenedispiro[2.0.2.1]heptane (4) (24% overall) or, more efficiently, through dehalogenative coupling of 7,7-dibromo[3]triangulane (15) (82%). This type of reductive dimerization turned out to be successful for the synthesis of (E)- and (Z)-bis(spiropentylidene) 14 (67%) and even of the "third-generation" spirocyclopropanated bicyclopropylidene 17 (17% overall from 15). Whereas the parent bicyclopropylidene 1 dimerized at 180 degrees C to yield [4]rotane, dimerization of 6 at 130 degrees C under 10 kbar pressure occured only with opening of one three-membered ring to yield the polyspirocyclopropanated (cyclopropylidene)cyclopentane derivative 19 (34% yield), and at the elevated temperature the polyspirocyclopropanated 2-cyclopropylidene[3.2.2]propellane derivative 20 (25 % yield). Perspirocyclopropanated bicyclopropylidene 6 and the "third-generation" bicyclopropylidene 17 gave addition of bromine, hydrogen bromide, and various dihalocarbenes without rearrangement. The functionally substituted branched [7]triangulane 28 and branched dichloro-C2v-[15]triangulane 32 were used to prepare the perspirocyclopropanated [3]rotane (D3h-[10]triangulane) 49 (six steps from 6, 1.4% overall yield) and the C2v-[15]triangulane 51 (two steps from 17, 41% overall). Upon catalytic hydrogenation, the perspirocyclopropanated bicyclopropylidene 6 yielded 7,7'-bis(dispiro[2.0.2.]-heptyl) (52) and, under more forcing conditions, 1,1'-bis(2,2,3,3-tetramethylcyclopropyl) (53). The bromofluorocarbene adduct 33 of 17 reacted with butyllithium to give the unexpected polyspirocyclopropanated 1,4-di-n-butyl-2-cyclopropylidenebicyclo[2.2.0]hexane derivative 37 as the main product (55% yield) along with the expected "third-generation" perspirocyclopropanated dicyclopropylidenemethane 38 (21% yield). Mechanistic aspects of this and the other unusual reactions are discussed. The structures of all new unusual hydrocarbons were proven by X-ray crystal structure analyses, and the most interesting structural and crystal packing features are presented.