Catalytic Activity of Molybdenum Complexes Bearing PNP-Type Pincer Ligand toward Ammonia Formation

We newly designed and prepared a novel molybdenum complex bearing a 4-[3,5-bis(trifluoromethyl)phenyl]pyridine-based PNP-type pincer ligand, based on the bond dissociation free energies (BDFEs) of the N−H bonds in molybdenum-imide complexes bearing various substituted pyridine-based PNP-type pincer ligands. The complex worked as an excellent catalyst toward ammonia formation from the reaction of an atmospheric pressure of dinitrogen with samarium diiodide as a reductant and water as a proton source under ambient reaction conditions, where up to 3580 equivalents of ammonia were formed based on the molybdenum atom of the catalyst. The catalytic activity was significantly improved by one order of magnitude larger than that observed when using the complex before modification.     

Enantioselective acylation of secondary alcohols catalyzed by chiral N-heterocyclic carbenes

[reaction: see text] The synthetic utility of chiral N-heterocyclic carbenes, which have been used mainly in transition metal-catalyzed reactions as a ligand, was demonstrated by the enantioselective acylation of secondary alcohols.     

Coexistence of solvated electrons and solvent valence anions in negatively charged acetonitrile clusters, (CH3CN)-n(n=10-100)

Anion photoelectron spectroscopy of acetonitrile cluster anions, (CH3CN)(-)(n) (n=10-100), successfully demonstrates the competitive coexistence of two different anionic species: a solvated electron and a solvent-bound valence anion. The distinctly different nature of these anions is revealed by hole-burning-type photoelectron spectroscopy and relative photodetachment cross section measurements. This unusual coexistence is attributed to the closely lying nature of their anionic states at just the number of solvent molecules sufficient to almost complete the first solvation layer.     

Spontaneous noise spectroscopy of an atomic magnetic resonance

We have experimentally demonstrated a new type of noise spectroscopy, which requires neither amplitude nor frequency noise of the light source. A highly stabilized diode laser provides low-noise light for the optical magnetic resonance of Rb atoms. The laser light transmitted through the Rb vapor contains significant intensity fluctuations whose power spectrum has a distinct peak at the Larmor frequency. The fluctuations are spontaneously generated by the atoms and are attributed to the stochastic properties of the photon scattering which randomly interrupts the Larmor precession of the atomic magnetic moment.     

Soft-landing isolation of vanadium-benzene sandwich clusters on a room-temperature substrate using n-alkanethiolate self-assembled monolayer matrixes

Gas-phase synthesized vanadium-benzene 1:2 (VBz(2)) sandwich clusters were size-selectively deposited onto bare gold and long-chain n-alkanethiolate [-S-(CH(2))(n-1)-CH(3); n = 16, 18, and 22] self-assembled monolayer (SAM)-coated gold substrates under ultrahigh vacuum (UHV) conditions. Investigation of the resulting deposited clusters was performed by infrared reflection absorption spectroscopy (IRAS) and thermal desorption spectroscopy (TDS). The IR frequencies of the soft-landed VBz(2) clusters show excellent agreement with the fundamentals reported in IR data of VBz(2) in an argon matrix. The analysis of IRAS spectra reveals that while there was no orientational preference of the VBz(2) clusters on a bare gold substrate, the VBz(2) clusters deposited onto the SAM substrates were highly oriented with the molecular axis 70-80 degrees tilted off the surface normal. In addition, analysis of TDS spectra revealed unusually large adsorption heats of the physisorbed VBz(2) clusters. The present results are explained by cluster penetration into the long-chain alkanethiolate SAM and for the first time demonstrate the matrix isolation of gas-phase organometallic clusters around room temperature.     

Molecular recognition of ketomalonates by asymmetric aldol reaction of aldehydes with secondary-amine organocatalysts

A diastereo- and enantioselective aldol reaction between aldehydes and a synthetically useful ketomalonate 1c as a hydrated form was developed, and either anti- or syn-aldol adducts having a chiral tetrasubstituted carbon center were obtained in high enantioselectivities by use of a tetrazole analogue of L-proline (S)-2 or an axially chiral amino sulfonamide (S)-3 as catalyst.     

Reaction of indium ate complexes with allylic compounds. Controlling SN2/SN2′ selectivity by solvents

Vinyl and methylindium ate complexes (indates) were prepared and both the tendency of immigration and regioselectivity toward cinnamyl bromide were investigated. The vinyl group was more preferably transferred than the Me group, giving a regioisomeric mixture of S_N2 and S_N2′ products. The ratio of S_N2/S_N2′ selectivity can be controlled by solvents; in the presence of polar solvents, such as N-butylpyrrolidone (NBP) and THF, the S_N2′ product was mainly obtained, whereas the S_N2 product was selectively prepared in solutions containing hexane. The vinylindium compound, generated by the reaction of allylic-type diindium reagents with imine, was also converted to the corresponding vinyl indate, which was allowed to react with allyl chloride to give a three-component coupling product.