Collision-energy-resolved Penning ionization electron spectroscopy of p-benzoquinone: study of electronic structure and anisotropic interaction with He(*)(2 (3)S) metastable atoms

Collision energy dependence of partial ionization cross sections (CEDPICS) of p-benzoquinone with He(*)(2 (3)S) metastable atoms indicates that interaction potentials between p-benzoquinone and He(*)(2 (3)S) are highly anisotropic in the studied collision energy range (100-250 meV). Attractive interactions were found around the C==O groups for in-plane and out-of-plane directions, while repulsive interactions were found around CH bonds and the benzenoid ring. Assignment of the first four ionic states of p-benzoquinone and an analogous methyl-substituted compound was examined with CEDPICS and anisotropic distributions of the corresponding two nonbonding oxygen orbitals (n(O) (+),n(O) (-)) and two pi(CC) orbitals (pi(CC) (+),pi(CC) (-)). An extra band that shows negative CEDPICS was observed at ca. 7.2 eV in Penning ionization electron spectrum.     

Enantioselective spiro ene-carbocyclization of 1,6-enynes catalyzed by tropos rhodium(I) complex with skewphos ligand

A tropos rhodium(I) complex having skewphos ligand is shown to be a highly enantioselective catalyst for asymmetric ene-type carbocyclization of 1,6-enynes with tri-substituted olefins to control quaternary stereogenic centers or spiro-rings.     

Catalytic intermolecular Pauson-Khand-type reaction: strong directing effect of pyridylsilyl and pyrimidylsilyl groups and isolation of Ru complexes relevant to catalytic reaction

Some circumstantial evidence for the directing effect of the 2-pyridylsilyl group in the Ru-catalyzed intermolecular Pauson-Khand-type reaction (PKR) of alkenyl(2-pyridyl)silane, alkyne, and carbon monoxide has been provided. Most importantly, we have succeeded in isolating several monometallic Ru complexes relevant to the catalytic reaction: Ru(vinylsilane)(CO)(3) complexes and ruthenacyclopentene. While the stoichimetric reaction of the Ru(vinylsilane)(CO)(3) complex with an alkyne led to the formation of the corresponding cyclopentenone (PKR product) at 100 degrees C, the ruthenacyclopentene intermediate was quantitatively produced at 50 degrees C. This complex was also converted to a cyclopentenone upon heating at 100 degrees C. Moreover, it was also found that the Ru(vinylsilane)(CO)(3) complex and ruthenacyclopentene serve as catalysts in intermolecular PKR.     

Spectroscopic identification of the CO-H2O 2-1 cluster trapped in an argon matrix

The infrared spectra of the carbon monoxide-water cluster as well as the CO monomer and dimer in an argon matrix at cryogenic temperatures have been reinvestigated on the basis of the isotope substitution experiment with 12CO and 13CO. Lines due to the CO-H2O 2-1 cluster in the matrix have been unambiguously identified in the CO and OH stretching regions. The isotope effect on the vibrational frequency of the cluster is observed in the CO stretching vibration but neither in the symmetric nor antisymmetric OH stretching vibrations. Each of the two vibrational lines due to the two CO vibrations of the CO-H2O 2-1 cluster is examined by comparing the expected spectral features at a 12CO/13CO ratio on a simulation with those observed experimentally. The migration of the trapped molecules (CO and H2O) in the matrix is discussed, in which the observed spectral change with the deposition temperature from 14 K to 30 K is explained.     

Racemic but tropos (chirally flexible) BIPHEP ligands for Rh(I)-complexes: highly enantioselective ene-type cyclization of 1,6-enynes

[reaction: see text] The tropos (chirally flexible) or atropos (chirally rigid) nature of BIPHEP-Rh complexes at room temperature critically depends on the amines complexed. The aliphatic DPEN complex is atropos, whereas the aromatic DABN complex is tropos. BIPHEP-Rh chirality can thus be controlled by DABN at room temperature. The amine-free BIPHEP-Rh complex is tropos. At 5 degrees C, even amine-free BIPHEP-Rh complexes are atropos and hence can be used as enantiopure catalysts to give high enantioselectivity in ene-type cyclization of 1,6-enynes.     

Preparation of multisubstituted allenes from allylsilanes

[reaction: see text] A three-step route of converting allylsilanes to functionalized allenes was developed. Thermal decomposition of 1,1-dibromo-2-(silylmethyl)cyclopropanes, which were quantitatively prepared by treatment of allylsilane derivatives with CHBr3/KO(t)Bu, afforded substituted 2-bromo-1,3-butadienes with elimination of bromosilanes. The Pd-catalyzed reaction of the bromodienes with soft nucleophiles gave the allene derivatives. Previously inaccessible tri- and tetrasubstituted allenes can be prepared by this method as well.     

Synthesis and structural, electronic, and optical properties of oligo(thienylfuran)s in comparison with oligothiophenes and oligofurans

[structure: see text] Alternate thiophene/furan oligomers having four and six heterocycles, i.e., oligo(thienylfuran) dimer and trimer 2 (n = 4 and 6), were newly synthesized by repetitive Stille coupling reactions. The structural, electronic, and optical properties of these oligomers were investigated by X-ray crystallography (for n = 4), cyclic voltammetry (CV), UV-vis and fluorescence spectroscopy, and DFT calculations, and the results were compared with those of corresponding oligothiophenes (1) and oligofurans (3). The inter-ring torsional energy profiles calculated for bithiophene 1 (n = 2), thienylfuran 2 (n = 2), and bifuran 3 (n = 2) at the B3LYP/6-31G(d) level indicated that the most stable conformers of 2 (n = 2) and 3 (n = 2) are fully coplanar with transoid structure while that of 1 (n = 2) is twisted with a dihedral angle of 158 degrees . In accord with this, X-ray crystallographic analysis of 2 (n = 4) revealed that the pi-conjugated system is nearly planar with the inter-ring C=C-C=C dihedral angles between the thiophene and furan rings of 173.6(7) degrees , -177.0(7) degrees , and 172.6(6) degrees . In the packing structure, these nearly planar molecules are arranged in a herringbone pattern. The CV on a series of oligo(thienylfuran)s 2 showed irreversible oxidation peaks at +0.90, +0.42, and +0.29 V vs Fc/Fc(+) for n = 2, 4, and 6, which were 0.15-0.18 V lower than those for corresponding oligothiophenes 1 and were closer to those for oligofurans 3. On the other hand, the UV-vis spectra of 2 showed the longest wavelength absorption to be almost identical with those of the corresponding 1, and more bathochromically shifted than those of the corresponding 3. The results of CV and UV-vis measurements were supported by DFT calculations (B3LYP/ 6-311+G(2d,p)//B3LYP/6-31G(d)). Thus, oligo(thienylfuran)s 2 have HOMOs which are higher than those of oligothiophenes 1 and close to those of 3, and HOMO-LUMO gaps which are close to those of 1 and smaller than those of 3. In fluorescence spectra, the quantum yield of 2 increased with elongation of the pi-system (n = 2 (3.5%), 4 (19%), 6 (24%)).     

Modes of conformational changes of proteins adsorbed on a planar hydrophobic polymer surface reflecting their adsorption behaviors

Infrared spectra of hen egg white lysozyme and bovine serum albumin (BSA) adsorbed on a solid poly tris(trimethylsiloxy)silylstyrene (pTSS) surface in D2O solution were measured using attenuated total reflection (ATR) Fourier transform infrared spectroscopy. From the area and shape of the amide I' band of each spectrum, the adsorption amount and the secondary structure were determined simultaneously, as a function of adsorption time. We could show that the average conformation for all the adsorbed lysozyme molecules was solely determined by the adsorption time, and independent of the bulk concentration, while the adsorption amount increased with the bulk concentration as well as the adsorption time. These results suggest that lysozyme molecules form discrete assemblies on the surface, and that the surface assemblies grow over several hours to have a definite architecture independent of the adsorption amount. As for BSA, the extent of the conformational change was solely determined by the adsorption amount, regardless of the bulk concentration and the adsorption time. These differences in the adsorption properties of lysozyme and BSA may reflect differences in their conformational stabilities.     

Methane Decomposition in a Barium Titanate Packed-Bed Nonthermal Plasma Reactor

The behavior of lattice oxygen species of the ferroelectric material during methane oxidation was investigated using a nonthermal plasma reactor packed with BaTiO ₃ pellets. Lattice oxygen species in BaTiO ₃ play an important role in the formation of N ₂ O and the oxidation of CH ₄ . The oxidation products such as CO and CO ₂ were formed from independent reaction pathways. Lattice oxygen species were able to preferentially oxidize the carbon species deposited on the pellet surface into CO. Also, N ₂ O and NO _x were independently formed in the N ₂–O ₂ reaction, suggesting that different oxygen species give N ₂ O and NO _x. N ₂ O was produced by the oxidation of molecular nitrogen with lattice oxygen species.     

Combination of sp2‐ and sp3‐Type Phosphorus Atoms for Gold Chemistry: Preparation,Structure, and Catalytic Activity of Gold Complexes That Bear Ligated 2‐Silyl‐1,3‐diphosphapropenes

Kinetically protected 2‐silyl‐1,3‐diphosphapropenes that bear both sp²‐ and sp³‐type phosphorus atoms were employed in the preparation of gold complexes. The structural properties of the 1,3‐diphosphapropene digold(I) complexes were characterized by spectroscopic and crystallographic analyses, which revealed unique aurophilic interactions and conformational properties of the ligand. The 2‐silyl‐1,3‐diphosphapropene‐bis(chlorogold) complexes catalyzed cycloisomerization reactions of 1,6‐enyne derivatives even in the absence of silver co‐catalyst, and were able to be recovered after the reaction. The catalytic activity of the digold complexes primarily depended on the sp²‐type phosphorus atom and the silyl group, and could be tuned by the sp³‐phosphino group. Additionally, results on the catalytic activity of the digold complex in the presence and absence of silver salts showed considerable differences.