CS2 Reductive Coupling to Acetylenedithiolate by a Dinuclear Ytterbium(II) Complex

The activation of CS₂ is of interest in a broad range of fields and, more particularly, in the context of creating new C−C bonds. The reaction of the dinuclear ytterbium(II) complex [Yb₂L₄], 1 , [L=(OtBu)₃SiO⁻] with carbon disulfide led to the isolation of unprecedented reduction products. In particular, the crystallographic characterization of complex [Yb₂L₄(μ-C₂S₂)], 2 , provided the first example of an acetylenedithiolate ligand formed from metal reduction of CS₂. Computational studies indicated that this unprecedented reactivity can be ascribed to the unusual binding mode of CS₂²⁻ in the isolated “key intermediate” [Yb₂L₄(μ-CS₂)], 3 , which results from the dinuclear nature of 1 .     

A Unified Approach to Local Quantum Uncertainty and Interferometric Power by Metric Adjusted Skew Information

Local quantum uncertainty and interferometric power were introduced by Girolami et al. as geometric quantifiers of quantum correlations. The aim of the present paper is to discuss their properties in a unified manner by means of the metric adjusted skew information defined by Hansen.     

The Early Steps of Molecule-to-Material Conversion in Chemical Vapor Deposition (CVD): A Case Study

Transition metal complexes with β-diketonate and diamine ligands are valuable precursors for chemical vapor deposition (CVD) of metal oxide nanomaterials, but the metal-ligand bond dissociation mechanism on the growth surface is not yet clarified in detail. We address this question by density functional theory (DFT) and ab initio molecular dynamics (AIMD) in combination with the Blue Moon (BM) statistical sampling approach. AIMD simulations of the Zn β-diketonate-diamine complex Zn(hfa)₂TMEDA (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA = N,N,N′,N′-tetramethylethylenediamine), an amenable precursor for the CVD of ZnO nanosystems, show that rolling diffusion of this precursor at 500 K on a hydroxylated silica slab leads to an octahedral-to-square pyramidal rearrangement of its molecular geometry. The free energy profile of the octahedral-to-square pyramidal conversion indicates that the process barrier (5.8 kcal/mol) is of the order of magnitude of the thermal energy at the operating temperature. The formation of hydrogen bonds with surface hydroxyl groups plays a key role in aiding the dissociation of a Zn-O bond. In the square-pyramidal complex, the Zn center has a free coordination position, which might promote the interaction with incoming reagents on the deposition surface. These results provide a valuable atomistic insight on the molecule-to-material conversion process which, in perspective, might help to tailor by design the first nucleation stages of the target ZnO-based nanostructures.     

Secondary Formation of Aromatic Nitroderivatives of Environmental Concern: Photonitration Processes Triggered by the Photolysis of Nitrate and Nitrite Ions in Aqueous Solution

Aromatic nitroderivatives are compounds of considerable environmental concern, because some of them are phytotoxic (especially the nitrophenols, and particularly 2,4-dinitrophenol), others are mutagenic and potentially carcinogenic (e.g., the nitroderivatives of polycyclic aromatic hydrocarbons, such as 1-nitropyrene), and all of them absorb sunlight as components of the brown carbon. The latter has the potential to affect the climatic feedback of atmospheric aerosols. Most nitroderivatives are secondarily formed in the environment and, among their possible formation processes, photonitration upon irradiation of nitrate or nitrite is an important pathway that has periodically gained considerable attention. However, photonitration triggered by nitrate and nitrite is a very complex process, because the two ionic species under irradiation produce a wide range of nitrating agents (such as ^•NO₂, HNO₂, HOONO, and H₂OONO⁺), which are affected by pH and the presence of organic compounds and, in turn, deeply affect the nitration of aromatic precursors. Moreover, aromatic substrates can highly differ in their reactivity towards the various photogenerated species, thereby providing different behaviours towards photonitration. Despite the high complexity, it is possible to rationalise the different photonitration pathways in a coherent framework. In this context, this review paper has the goal of providing the reader with a guide on what to expect from the photonitration process under different conditions, how to study it, and how to determine which pathway(s) are prevailing in the formation of the observed nitroderivatives.     

Effect of limonene on the frontal ring opening metathesis polymerization of dicyclopentadiene

The frontal ring opening metathesis polymerization (FROMP) of dicyclopentadiene (DCPD) in the presence of limonene, using second generation Grubbs’ catalysts, is reported. The effect of limonene on the amount of catalyst and the typical frontal polymerization parameters, as maximum temperature (T_max) and velocity of the front (V_f), is studied. In addition, the influence of limonene on the mechanical properties of the polymeric samples is reported. Finally, a deep study on the swelling properties of polymers is done. It has been demonstrated that limonene acts as both inhibitor and solvent of the catalyst. The T_max, V_f, T_g, and Young modulus values decrease as the amount of limonene increases, and the polymer samples swell in THF depending on the amount of limonene. All results indicate that the limonene addition on FROMP of results in advantages on the polymerization reaction and its parameters and on the final polymer properties. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 63–68     

Extremal Curves in Nilpotent Lie Groups

We classify extremal curves in free nilpotent Lie groups. The classification is obtained via an explicit integration of the adjoint equation in Pontryagin maximum principle. It turns out that abnormal extremals are precisely the horizontal curves contained in algebraic varieties of a specific type. We also extend the results to the nonfree case.