Benzoyl(acetylacetonato)nickel(II) complexes containing tertiary phosphine ligands. Their synthesis,dynamic behavior in solution,and decarbonylation

Carbon monoxide is readily inserted into the phenyl—nickel bond of PhNi(acac)(PR₃)_n to give benzoylnickel complexes, PhCONi(acac)PR₃ (R = Ph, Et, cyclo-C₆H₁₁), which were characterized by elemental analysis, IR and NMR spectroscopy, as well as chemical reactions. The reactions of the benzoylnickel complexes with methyl iodide and alcohols give acetophenone and corresponding benzoates, respectively, accompanied by some decomposition reactions. The solid benzoylnickel complexes when heated at elevated temperatures are decarbonylated and biphenyl, benzophenone and carbon monoxide are liberated. The dynamic behavior of the acac ligand in acetone solution was studied and the activation parameters for the acac exchange reactions were obtained. The decarbonylation reaction of the benzoyl complex PhCONi(acac)PPh₃ in acetone was studied by NMR, and found to be first order in the benzoylnickel complex.     

Theoretical study of benzonitrile clusters in the gas phase and their adsorption onto a Au(111) surface

We made theoretical calculations for a benzonitrile molecule and its clusters in the gas phase and as adsorbed on the Au(111) surface, to explain the observation by scanning tunneling microscope, that is, the trimer formation of cyanophenyl porphyrins adsorbed onto the Au(111) surface. With regard to the gas-phase species, ab initio calculations showed that (1) the benzonitrile dimer has a single stable structure that is planar and antiparallel; (2) the trimer has two isoenergetic stable structures, that is, a planar and cyclic structure and an antiparallel and nonplanar one; (3) the clusters are more stable, at low temperatures, than the monomer. For the adsorbed species, we made quantum mechanical/molecular mechanical calculations in which the interaction between the adsorbates and the surface is evaluated in a molecular-mechanical way by using analytical potential functions and an image charge model. Because the stable structures were found to be similar to those in the gas phase, the cluster formation of adsorbed cyanophenyl porphyrins was attributed to the interaction between cyanophenyl groups, which is barely affected by adsorbate-surface interaction. It was also found that the adsorbed cyclic benzonitrile trimer is more stable than the monomer and the dimer because the relative stability is dependent on enthalpy alone. We therefore concluded that the preferential formation of trimers by the adsorbed cyanophenyl porphyrins is due to the negligible contribution of entropy to the relative stability of the adsorbed species and that the adsorption hardly changes the situation found in the gas phase.     

Blue myoglobin reconstituted with an iron porphycene shows extremely high oxygen affinity

Myoglobin will be a good scaffold for engineering a function into proteins. To modulate the physiological function of myoglobin, almost all approaches have been demonstrated by site-directed mutagenesis, however, there are few studies which show a significant improvement in the function. In contrast, we focused on the replacement of heme in the protein with an artificial prosthetic group. Recently, we prepared a novel myoglobin reconstituted with an iron porphycene as a structural isomer of mesoheme. The bluish colored reconstituted myoglobin is relatively stable and the deoxymyoglobin reversibly binds ligands. Interestingly, the O2 affinity of the reconstituted myoglobin, 1.1 x 109 M-1, is a significant 1,400-fold higher than that of the native myoglobin. Furthermore, the unfavorable autoxidation kinetics show 7-fold decrease in rate for the reconstituted myoglobin relative to the native myoglobin, indicating the stable oxy-form against autoxidation. The net results come from the slow dissociation of the O2 ligand in the reconstituted myoglobin, koff = 0.11 s-1, because of the formation of strong hydrogen bond between His64 and negatively charged dioxygen. The present study indicates that the replacement of native heme with an artificially created prosthetic group will give us a unique function into a hemoprotein.     

Microbiological synthesis of 16-ketopregnanes from steroidal sapogenins

Incubation of diosgenone (1, 25D-spirost-4-en-3-one) with Verticillium theobromae (Turconi) Mason et Hughes (CBS) afforded 20α-hydroxypregn-4<ne-3,16-dione (3) and 3α,11β,20α-trihydroxy-5α-pregnan-16-one (4). The same transformation products were also obtained by the use of Stachylidium bicolor Link (IFO 6647). Isolation and identification processes of the products are discussed.     

On the topology of compact smooth three-dimensional Levi-flat hypersurfaces

We study topological conditions that must be satisfied by a compactC ^∞ Levi-flat hypersurface in a two-dimensional complex manifold, as well as related questions about the holonomy of Levi-flat hypersurfaces. As a consequence of our work, we show that no two-dimensional complex manifold admits a subdomain Ω with compact nonemptyC ^∞ boundary such that Ω ? ?².     

Synthesis of optically active pheromones with an epoxy ring, (+)-disparlure and the saltmarsh caterpillar moth pheromone [(Z,Z)-3,6-cis-1-9,10-epoxyheneicosadiene]

(+)-Disparlure $\text{2}$, and the saltmarsh caterpillar moth pheromone enantiomers $\text{1}$ were synthesized and the stereochemistry of the naturally occurring $\text{1}$ was shown to be 9$\text{S}$, 1O$\text{R}$.     

Mononuclear five-coordinate molybdenum(IV) and -(V) monosulfide complexes coordinated with dithiolene ligands: reversible redox of Mo(V)/Mo(IV) and irreversible dimerization of [MoVS]- cores to a dinuclear [MoV2(mu-S)2]2- Core

A mononuclear five-coordinate molybdenum(IV) monosulfide complex, (Et4N)2[MoS(L)2] (L = cyclohexene-1,2-dithiolate) (1), was obtained and characterized by IR, UV-vis spectroscopic methods, and X-ray crystallography. 1 was oxidized by an equivalent ferrocenium cation to give the corresponding mononuclear molybdenum(V) complex, (Et4N)[MoS(L)2] (2), which was stable for a few minutes under a lower concentration than 0.3 mM and then further dimerized to (Et4N)2[Mo(L)2]2(mu-S)2 (3).     

Direct observation of adduct formation of alkyl and aromatic iodides with cl atoms using cavity ring-down spectroscopy

The reactions of Cl atoms with RI (R = n-C3H7, n-C4H9, cyclo-C6H11, C6H5, C6F5, and p-CH3C6H4) have been studied using cavity ring-down spectroscopy at a temperature range of 233-313 K and at 100 Torr total pressure of N2 diluent. Visible absorption spectra of the RI-Cl adducts were recorded at 440-520 nm at 263 K. The yields of the adducts were temperature-dependent. There was no discernible reaction of the adducts in the presence of 100 Torr of O2 at 263 K. Theoretical calculations were performed for C4H9I-Cl and C6H5I-Cl for quantitative explanation of the absorption spectra and the strength of the I-Cl bonds in the charge-transfer complexes. Evidence for the adduct formation following the reaction of Cl with C6H5Br was sought but not found at 440 and 520 nm.     

Kunzeanones A, B, and C: novel alkylated phloroglucinol metabolites from Kunzea ambigua

Three new metabolites, kunzeanones A (1), B (2), and C (3), along with three known compounds, cryptostrobin (4), (+)-spathulenol (5), and (−)-globulol (6), were isolated from the non-polar fraction of the dried leaves of Kunzea ambigua (Myrtaceae), which shows ichthyotoxicity toward a small fish, medaka. The structures of these new compounds were elucidated as condensates of alkylated phloroglucinol with methylflavanone and germacrane-type sesquiterpene, respectively, on the basis of spectral analyses including 1-D and 2-D NMR spectra. The stereochemistries of kunzeanones A and B were determined by X-ray crystallographic analysis. A sesquiterpene, (+)-spathulenol (5), among the isolates was characterized as the ichthyotoxic principle of the extract.     

Abnormal Li diffusion in β-LiGa by the formation of defect complex

The diffusion coefficients of Li in the NaTl-type Li intermetallic compound of β-LiGa have been measured by using a short-lived radioactive diffusion tracer. As the tracer, the α-emitting radioisotope of ⁸Li delivered as the energetic and pulsed beam from Tokai Radioactive Ion Accelerator Complex (TRIAC) was implanted into the β-LiGa compounds with the composition in the range of about 43 to 54 at.% Li. By analyzing the time-dependent yields of the α-particles measured according to the repetition cycle of the beam, the tracer diffusion coefficients were extracted over the wide range of Li composition. Abnormal composition-dependence of Li diffusion coefficients in β-LiGa was observed; the stoichiometric β-LiGa showed the highest diffusivity of Li. By referring to the composition-dependent diffusivity of Li in the iso-structural β-LiAl and β-LiIn, we could identify the abnormal diffusion of Li in very Li-poor composition of β-LiGa. The anomaly has been discussed qualitatively in terms of the formation of defect complex and the interaction between the constitutional defects.