An isoxazole strategy for the synthesis of 4-oxo-1,4-dihydropyridine-3-carboxylates.

A method has been developed for the preparation of 2-alkyl-6-aryl-, 2-aryl-6-aryl and 2,6-diaryl-5-aryl/hetaryl-substituted methyl 4-oxo-1,4-dihydropyridine-3-carboxylates by Mo(CO)6-mediated ring expansion of methyl 2-(isoxazol-5-yl)-3-oxopropanoates. The high reactivity of 4-oxo-1,4-dihydropyridine-3-carboxylates synthesized provide easy access to 2,4,6-triaryl-substituted and 1,2,5,6-tetrasubstituted nicotinates.

Low-energy electron interaction and focused electron beam-induced deposition of molybdenum hexacarbonyl (Mo(CO)6).

Motivated by the potential role of molybdenum in semiconductor materials, we present a combined theoretical and experimental gas-phase study on dissociative electron attachment (DEA) and dissociative ionization (DI) of Mo(CO)6 in comparison to focused electron beam-induced deposition (FEBID) of this precursor. The DEA and DI experiments are compared to previous work, differences are addressed, and the nature of the underlying resonances leading to the observed DEA processes are discussed in relation to an earlier electron transmission study. Relative contributions of individual ionic species obtained through DEA and DI of Mo(CO)6 and the average CO loss per incident are calculated and compared to the composition of the FEBID deposits produced. These are also compared to gas phase, surface science and deposition studies on W(CO)6 and we hypothesize that reductive ligand loss through electron attachment may promote metal-metal bond formation in the deposition process, leading to further ligand loss and the high metal content observed in FEBID for both these compounds.

Formation of Pt-Based Alloy Nanoparticles Assisted by Molybdenum Hexacarbonyl.

We report on an optimized, scalable solution-phase synthetic procedure for the fabrication of fine-tuned monodisperse nanostructures (Pt(NiCo), PtNi and PtCo). The influence of different solute metal precursors and surfactants on the morphological evolution of homogeneous alloy nanoparticles (NPs) has been investigated. Molybdenum hexacarbonyl (Mo(CO)6) was used as the reductant. We demonstrate that this solution-based strategy results in uniform-sized NPs, the morphology of which can be manipulated by appropriate selection of surfactants and solute metal precursors. Co-surfactants (oleylamine, OAm, and hexadecylamine, HDA) enabled the development of a variety of high-index faceted NP morphologies with varying degrees of curvatures while pure OAm selectively produced octahedral NP morphologies. This Mo(CO)6-based synthetic protocol offers new avenues for the fabrication of multi-structured alloy NPs as high-performance electrocatalysts.

Mechanochemical Palladium-Catalyzed Carbonylative Reactions Using Mo(CO)6.

Esters and amides were mechanochemically prepared by palladium-catalyzed carbonylative reactions of aryl iodides by using molybdenum hexacarbonyl as a convenient solid carbonyl source and avoiding a direct handling of gaseous carbon monoxide. Real-time monitoring of the mechanochemical reaction by in situ pressure sensing revealed that CO is rapidly transferred from Mo(CO)6 to the active catalytic system without significant release of molecular carbon monoxide.

Palladium-catalyzed thio- and selenocarbonylation of 2-iodoglycals

The carbonylative cross-coupling reactions of 2-iodoglycals with thiols and selenols in the presence of molybdenum hexacarbonyl as a solid source of carbon monoxide is described. This methodology permitted the synthesis of 29 C2-glycosides bearing thioester and selenoester functionalities in moderate to excellent yields and high functional group tolerance. Moreover, this communication describes the first catalytic carbonylative coupling reaction of selenols with a carbon electrophile.

Highly Uniform Atomic Layer-Deposited MoS2@3D-Ni-Foam: A Novel Approach To Prepare an Electrode for Supercapacitors.

This article takes an effort to establish the potential of atomic layer deposition (ALD) technique toward the field of supercapacitors by preparing molybdenum disulfide (MoS2) as its electrode. While molybdenum hexacarbonyl [Mo(CO)6] serves as a novel precursor toward the low-temperature synthesis of ALD-grown MoS2, H2S plasma helps to deposit its polycrystalline phase at 200 °C. Several ex situ characterizations such as X-ray diffractometry (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and so forth are performed in detail to study the as-grown MoS2 film on a Si/SiO2 substrate. While stoichiometric MoS2 with very negligible amount of C and O impurities was evident from XPS, the XRD and high-resolution transmission electron microscopy analyses confirmed the (002)-oriented polycrystalline h-MoS2 phase of the as-grown film. A comparative study of ALD-grown MoS2 as a supercapacitor electrode on 2-dimensional stainless steel and on 3-dimensional (3D) Ni-foam substrates clearly reflects the advantage and the potential of ALD for growing a uniform and conformal electrode material on a 3D-scaffold layer. Cyclic voltammetry measurements showed both double-layer capacitance and capacitance contributed by the faradic reaction at the MoS2 electrode surface. The optimum number of ALD cycles was also found out for achieving maximum capacitance for such a MoS2@3D-Ni-foam electrode. A record high areal capacitance of 3400 mF/cm2 was achieved for MoS2@3D-Ni-foam grown by 400 ALD cycles at a current density of 3 mA/cm2. Moreover, the ALD-grown MoS2@3D-Ni-foam composite also retains high areal capacitance, even up to a high current density of 50 mA/cm2. Finally, this directly grown MoS2 electrode on 3D-Ni-foam by ALD shows high cyclic stability (>80%) over 4500 charge-discharge cycles which must invoke the research community to further explore the potential of ALD for such applications.