Crossed molecular beams study on the formation of vinylacetylene in Titan's atmosphere.

The reaction of ground-state ethynyl radicals, C(2)H(X(2)Sigma(+)), with d(4)-ethylene, C(2)D(4)(X(1)A(g)), was investigated at a collision energy of 20.6 +/- 0.4 kJ mol(-1) utilizing the crossed-beams technique. Combined with electronic structure calculations, our results elucidate that this reaction follows indirect reaction dynamics via a doublet radical complex. The reaction is initiated by a barrierless addition of the ethynyl radical to a carbon atom of the d(4)-ethylene molecule to form a C(4)HD(4) intermediate. The latter is long-lived compared with its rotational period and decomposes via a tight exit transition state to form the d(3)-vinylacetylene product (HCCC(2)D(3)) plus a deuterium atom while conserving the ethynyl group; the center-of-mass angular distribution suggests that the deuterium atom leaves almost perpendicularly to the rotational plane of the fragmenting C(4)HD(4) complex. The overall reaction is found to be exoergic by 94 +/- 20 kJ mol(-1); this value agrees nicely with a computational data of 103 +/- 5 kJ mol(-1). This study indicates that the analogous vinylacetylene molecule (HCCC(2)H(3)) can be synthesized in a low-temperature environment such as Titan's atmosphere via the neutral-neutral reaction of ethynyl radicals with ubiquitous ethylene. The similarity between this reaction and that of the isoelectronic cyano radical, CN(X(2)Sigma(+)), with ethylene-yielding vinylcyanide (C(2)H(3)CN) is also discussed.

The Bis(pentafluoroethyl)phosphinous acid (C2F5)2POH.

The industrial product (C(2)F(5))(3)PF(2) is transformed into the phosphinic acid chloride (C(2)F(5))(2)P(O)Cl, which reacts with an excess of Bu(3)SnH in a clean, multistep reaction to give the stannyl derivative (C(2)F(5))(2)POSnBu(3). Subsequent treatment with gaseous HBr leads to the formation of (C(2)F(5))(2)POH, which is isolated in 70 % yield. Besides (CF(3))(2)POH, bis(pentafluoroethyl)phosphinous acid, (C(2)F(5))(2)POH, represents the second known example of a phosphinous acid that is predicted by using density functional theory calculations at the B3PW91/6-311G(3d,p) level to be more stable than the phosphane oxide tautomer, the energy difference being 11.7 kJ mol(-1). Only the phosphinous acid isomer is detectable in the gas phase and in solution. However, investigations of the neat liquid reveal a temperature-dependent tautomeric equilibrium with the phosphane oxide isomer (C(2)F(5))(2)P(O)H, which is characterized by vibrational and multinuclear NMR spectroscopic methods in combination with quantum-chemical calculations.

A crossed molecular beam study on the synthesis of the interstellar 2,4-pentadiynylidyne radical (HCCCCC).

Crossed molecular beam experiments are performed to elucidate the synthesis of the 2,4-penta-diynylidyne [HCCCCC(X (2)Pi)] radical under single collision conditions--a crucial reaction intermediate to form polycyclic aromatic hydrocarbons and carbonaceous nanostructures in the interstellar medium and in combustion flames. The experiments demonstrate that the chemical dynamics of ground state carbon reacting with diacetylene [HCCCCH(X (1)Sigma(g)(+))] are indirect and proceed via addition of the electrophilic carbon atom to the pi electron density of the diacetylene molecule yielding ultimately the carbenelike HCCCCCH(X (3)Sigma(g)(-)) molecule. This intermediate fragments via hydrogen atom emission to yield the 2,4-pentadiynylidyne [HCCCCC(X (2)Pi)] radical. The chemical dynamics elucidated also allows us to predict that reaction of carbon atoms with polyynes of the generic formula H(C[triple bond]C)(n)H leads to the formation of hydrogen-terminated carbon clusters of the generic form HC(2n+1) in extreme environments. The acetylene-related reactivity and electronic structure of the diacetylene molecule also allow us to project that reactions of the diacetylene molecule with cyano and ethynyl radicals result in a stepwise extension of the carbon skeleton forming cyanodiacetylene (HCCCCCN) and triacetylene (HCCCCCCH) plus atomic hydrogen. These predictions open the door to extensive laboratory studies involving hitherto poorly understood reactions of the diacetylene molecule under single collision conditions.

Infrared spectrum of matrix isolated selenoformaldehyde, CH2Se, and CD2Se.

Thermolysis of highly diluted (CH2Se)3 or (CD2Se)3 in a flow of argon with subsequent quenching of the products in an matrix at 15 K yields monomeric CH2Se and CD2Se, respectively. Six fundamental vibrations upsilon1 = 2972.5, upsilon2 = 1413.3, upsilon3 = 854.2, upsilon4 = 916.4, upsilon 5 = 3052.9, and upsilon 6 = 913.2 cm(-1) and two combination bands have been observed for CH2Se as well as three fundamentals of CD2Se. The vibrational wavenumbers are compared with those of CH2O and CH2S. Matrix isolated selenoformaldehyde decomposes slowly by UV photolysis to yield the CSe molecule.

Organic glass-forming materials: 1,3,5-tris(naphthyl)benzene derivatives.

The organic glass-forming materials 1,3-bis(1-naphthyl)-5-(2-naphthyl)benzene (2) and its partially deuterated analogue, 1,3-bis(1-naphthyl-d(7))-5-(2-naphthyl)benzene (2-d(14)), have been synthesized on a gram scale using Suzuki coupling reactions. Detailed spectroscopic studies afford complete NMR assignments (1H, 2H, 13C) for both compounds. Modest energy barriers for the interconversion of atropisomers (ca. 15 kcal/mol) result in a propensity for these materials to form supercooled liquids and glasses, rather than undergoing crystallization. The preparation of these materials enables detailed studies of physical properties of organic glasses and molecular diffusion in condensed phases.

Organic glasses with exceptional thermodynamic and kinetic stability.

Vapor deposition has been used to create glassy materials with extraordinary thermodynamic and kinetic stability and high density. For glasses prepared from indomethacin or 1,3-bis-(1-naphthyl)-5-(2-naphthyl)benzene, stability is optimized when deposition occurs on substrates at a temperature of 50 K below the conventional glass transition temperature. We attribute the substantial improvement in thermodynamic and kinetic properties to enhanced mobility within a few nanometers of the glass surface during deposition. This technique provides an efficient means of producing glassy materials that are low on the energy landscape and could affect technologies such as amorphous pharmaceuticals.

Ring opening of 2,5-didehydrothiophene: matrix photochemistry of C4H2S isomers.

Irradiation (lambda > 254 nm) of matrix-isolated 2,5-diiodothiophene (10) gives rise to IR bands assigned to ethynylthioketene (6). Diethynyl sulfide (3), which would form in the process of retro-Bergman cyclization of the incipient 2,5-didehydrothiophene (4), is not detected. Under the same irradiation conditions, matrix-isolated diethynyl sulfide (3) rearranges to thioketene 6 and butatrienethione (5), the global minimum on C4H2S potential energy surface. The photochemical formation of thioketene 6 from either diyl 4 or sulfide 3 may be interpreted in line with a recent computational prediction on the thermal ring opening of diyl 4, which favors C-S bond cleavage, leading to 6, over C-C bond cleavage, leading to 3. Photolysis of matrix-isolated 3,4-thiophenedicarboxylic acid anhydride (11) enables the observation of the photoequilibration of three low-energy C4H2S isomers, butatrienethione (5), ethynylthioketene (6), and butadiynylthiol (7), via apparent [1,3]-hydrogen shifts.

Neutron reflectivity measurements of the translational motion of tris(naphthylbenzene) at the glass transition temperature.

The translational dynamics of the low molecular weight glass-former tris(naphthylbenzene) have been studied on the length scale of a few nanometers at the glass transition temperature Tg. Neutron reflectivity was used to measure isotopic interdiffusion of multilayer samples created by physical vapor deposition. Deposition with the substrate held at Tg-6 K allows observation of dynamics characterizing the equilibrium supercooled liquid. The diffusion coefficient measured at q = 0.03 A(-1) was determined to be 1x10(-17) cm2/s at 342 K (Tg). The self-part of the intermediate scattering function I(s)(q,t) decays exponentially. Samples deposited well below Tg show a substantial thermal history effect during subsequent translational motion at Tg.

Ring opening of 2,5-didehydrothiophene: structures and rearrangements of C4H2S isomers.

Electronic structures and rearrangement pathways of several C4H2S isomers are computationally investigated by methods based on coupled cluster theory and density functional theory. Six singlet C4H2S isomers lie within ca. 30 kcal/mol above butatrienethione (6), the apparent global minimum. Ethynylthioketene (7) lies only 2 kcal/mol higher in energy than cumulene 6. Two open-chain isomers, butadiynylthiol (8) and diethynyl sulfide (9), reside ca. 9 and 24 kcal/mol above 6, respectively. Lying 30 kcal/mol above 6, two cyclic singlet isomers, ethynylthiirene (10) and cyclopropenylidenemethanthione (11), are nearly degenerate in energy. Thiophene-2,5-diyl (12) lies substantially higher in energy than 6 (ca. 45 kcal/mol) and is predicted to rearrange preferentially by C-S bond cleavage, leading to thioketene 7, rather than by C-C bond cleavage, leading to diethynyl sulfide (9; retro-Bergman cyclization). Accurate spectroscopic properties of these C4H2S isomers, as well as an understanding of their rearrangement pathways, should facilitate the detection and characterization of these isomers in the laboratory and the interstellar medium.

Access to the naphthylcarbene rearrangement manifold via isomeric benzodiazocycloheptatrienes.

Irradiation (lambda = 670 or >613 nm) of 4,5-benzodiazocycloheptatriene (15), matrix isolated in argon at 10 K, produces primarily 2,3-benzobicyclo[4.1.0]hepta-2,4,6-triene (9) accompanied by small amounts of triplet 4,5-benzocycloheptatrienylidene (2) and 2-naphthylcarbene (10). A reversible photoequilibrium is established in which 9 is converted to 10 at lambda = 290 nm and then regenerated at lambda = 360 nm. Similarly, matrix-isolated 2,3-benzodiazocycloheptatriene (16) produces 4,5-benzobicyclo[4.1.0]hepta-2,4,6-triene (11) at lambda = 670 or >613 nm, but without detection of 2,3-benzocycloheptatrienylidene (4). Irradiation of 11 at lambda = 290 nm induces ring opening to triplet 1-naphthylcarbene (12), which, in turn, cyclizes back to 11 at lambda = 342 or >497 nm. The diazo compounds and photoproducts are characterized by IR, UV/visible, and ESR spectroscopy, where appropriate, and by comparison of the experimental and B3LYP/6-31G calculated IR spectra for each species. Alternate rearrangement products such as allenes 6, 7, and 8 are not detected in the photolysis of either diazo compound.