Contrasting Structure and Bonding of a Copper-Rich and a Zinc-Rich Intermetalloid Cu/Zn Cluster.

Reaction of the Cu(I) sources, [Cu5](Mes)5 and [(iDipp)CuOtBu] (Mes = mesityl; iDipp = 1,3-bis(2,6-diisopropylphenyl)-1H-imidazol-2-ylidene) with the Zn(I) complex [Zn2](Cp*)2 leads to a mixture of intermetallic Cu/Zn clusters with a distribution of species that is dependent on the stoichiometric ratio of the reactants, the reaction time, as well as the temperature. Systematic and careful investigation of the product mixtures rendered the isolation of two new clusters possible, i.e., the Zn-rich, red cluster 1, [CuZn10](Cp*)7 = [Cu(ZnZnCp*)3(ZnCp*)4], as well as the Cu-rich, dark-green cluster 2 [Cu10Zn2](Mes)6(Cp*)2. Structure and bonding of these two species was rationalized with the help of density functional theory calculations. Whereas 1 can be viewed as an 18-electron Cu center coordinated to four ZnCp* and three ZnZnCp* one-electron ligands (with some interligand bonding interaction), compound 2 is better to be described as a six-electron superatom cluster. This unusual electron count is associated with a prolate distortion from a spherical superatom structure. This unexpected situation is likely to be associated with the ZnCp* capping units that offer the possibility to strongly bind to the top and the bottom of the cluster in addition to the bridging mesityl ligands stabilizing the Cu core of the cluster.

Edge, size, and shape effects on WS2, WSe2, and WTe2 nanoflake stability: design principles from an ab initio investigation.

An improved atomistic understanding of the W-based two-dimensional transition-metal dichalcogenides (2D TMDs) is crucial for technological applications of 2D materials, since the presence of tungsten endows these materials with distinctive properties. However, our atomistic knowledge on the evolution of the structural, electronic, and energetic properties and on the nanoflake stability of such materials is not properly addressed hitherto. Thus, we present a density functional theory (DFT) study of stoichiometric (WQ2)n nanoflakes, with Q = S, Se, Te, and n = 1,…,16, 36, 66, and 105. We obtained the configurations with n = 1,…,16 through the tree growth algorithm whereas the nanoflakes with n = 36, 66, and 105 were generated from fragments of 2D TMDs with an abundant diversity of shapes and edge configurations. We found that all the most stable nanoflakes present the same Q-terminated edge configuration. Furthermore, in isomers with n = 1,…,16 sizes, nanoflakes with triangular shapes and their derivatives, such as the rhombus geometry, define magic numbers, whereas for n > 16, triangular shapes were also found for the most stable structures, because they preserve the edge configuration. A strong modulation of the Hirshfeld charges, depending on chalcogen species and core or edge position, is also observed. The modulation of the Hirshfeld charge due to the nature of the W metal atoms makes the energetic 1D → 1T' transition of (WQ2)n differ in nanoflake size in relation to (MoQ2)n nanoflakes. Our analysis shows the interplay between edge configuration, coordination environment, and shape that determines the stability of nanoflakes, and allows us to describe design principles for stable 1T' stoichiometric nanoflakes of various sizes.

The Mackay-Type Cluster [Cu43 Al12 ](Cp*)12 : Open-Shell 67-Electron Superatom with Emerging Metal-Like Electronic Structure.

The paramagnetic cluster [Cu43 Al12 ](Cp*)12 was obtained from the reaction of [CuMes]5 and [AlCp*]4 (Cp*=η5 -C5 Me5 ; Mes=mesityl). This all-hydrocarbon ligand-stabilized M55 magic atom-number cluster features a Mackay-type nested icosahedral structure. Its open-shell 67-electron superatom configuration is unique. Three unpaired electrons occupy weakly antibonding jellium states. The situation prefigures the formation of a conduction band, which is in line with the measured temperature-independent magnetism. Steric protection by twelve Cp* ligands suppresses the intrinsic polyradicalar reactivity of the Cu43 Al12 core.

Unexpected NO transfer reaction between trans-[Ru(II)(NO+)(NH3)4(L)]3+ and Fe(III) species: observation of a heterobimetallic NO-bridged intermediate.

The reaction between trans-[Ru(II)(NO(+))(NH3)4(L)](3+), L = ImN, IsN, Nic, P(OMe)3, P(OEt)3, and P(OH)(OEt)2, and the Fe(III) species [Fe(III)(TPPS)], metmyoglobin, and hemoglobin was monitored by UV-vis, EPR, and electrochemical techniques (DPV, CV). No reaction was observed when L = ImN, IsN, Nic, and P(OH)(OEt)2. However, when L = P(OMe)3 and P(OEt)3, the reaction was quantitative and the products were trans-[Ru(III)(H2O)(NH3)4(P(OR)3)](3+) and [Fe(II)(NO(+))] species. Reaction kinetics data and DFT calculations suggest a two-step reaction mechanism with the initial formation of a bridged [Ru-(µNO)-Fe] intermediate, which was confirmed through electrochemical techniques (E(0)' = -0.47 V vs NHE). The calculated specific rate constant values for the reaction were in the ranges k1 = 1.1 to 7.7 L mol(-1) s(-1) and k2 = 2.4 × 10(-3) to 11.4 × 10(-3) s(-1) for L = P(OMe)3 and P(OEt)3. The oxidation of the ruthenium center (Ru(II) to Ru(III)) containing the nitrosonium ligand suggests that NO can act as an electron transfer bridge between the two metal centers.

Assignment of individual structures from intermetalloid nickel gallium cluster ensembles.

Poorly selective mixed-metal cluster synthesis and separation yield reaction solutions of inseparable intermetalloid cluster mixtures, which are often discarded. High-resolution mass spectrometry, however, can provide precise compositional data of such product mixtures. Structure assignments can be achieved by advanced computational screening and consideration of the complete structural space. Here, we experimentally verify structure and composition of a whole cluster ensemble by combining a set of spectroscopic techniques. Our study case are the very similar nickel/gallium clusters of M12, M13 and M14 core composition Ni6+xGa6+y (x + y ≤ 2). The rationalization of structure, bonding and reactivity is built upon the organometallic superatom cluster [Ni6Ga6](Cp*)6 = [Ga6](NiCp*)6 (1; Cp* = C5Me5). The structural conclusions are validated by reactivity tests using carbon monoxide, which selectively binds to Ni sites, whereas (triisopropylsilyl)acetylene selectively binds to Ga sites.

Nitroxyl as a ligand in ruthenium tetraammine systems: a density functional theory study.

The properties of the free nitroxyl molecule and the nitroxyl ligand in Ru(ii) tetraammines (trans-[Ru(NH3)4(nitroxyl)(n)(L)](2+n) (n = nitroxyl charge; L = NH3, py, P(OEt)3, H2O, Cl(-) and Br(-))) were studied using density functional theory. According to the calculated conformational energies, HNO complexes are more stable than their deprotonated analogues, and the singlet configuration (trans-(1)[Ru(NH3)4(L)HNO](2+)) is lower in energy than the corresponding triplet (trans-(3)[Ru(NH3)4(L)HNO](2+)). An evaluation of the σ and π components of the L-Ru-HNO bond suggest that the increased stability of these orbitals and the enhanced contributions from the HNO orbitals correlate to shorter Ru-N(H)O distances and higher νRu-HNO stretching frequencies. The stability of the Ru-HNO bond was also evaluated through a theoretical kinetic study of HNO dissociation from trans-(1)[Ru(NH3)4(L)HNO](2+). The order of the Ru-HNO bonding stability in trans-(1)[Ru(NH3)4(L)HNO](2+) as a function of L was found to be as follows: H2O > Cl(-)∼ Br(-) > NH3 > py > P(OEt)3. This order parallels the order of the trans-effect and trans-influence series experimentally measured for L in octahedral complexes. The same trend was also observed using an explicit solvent model, considering the presence of both HNO and H2O molecules in the transition state. For this series, the calculated bond dissociation enthalpies for the Ru-HNO bonds are in the range 23.8 to 45.7 kcal mol(-1). A good agreement was observed between the calculated ΔG(‡) values for the displacement of HNO by H2O in trans-(1)[Ru(NH3)4(P(OEt)3HNO](2+) (23.4 kcal mol(-1)) and the available experimental data for the substitution reactions of trans[Ru(NH3)4(POEt)3(Lx)](2+) (19.4 to 24.0 kcal mol(-1) for Lx = isn and P(OET)3, respectively).

Cyanate as an Active Precursor of Ethyl Carbamate Formation in Sugar Cane Spirit.

The thermodynamic and kinetic aspects of ethyl carbamate (EC) formation through the reaction between cyanate and ethanol were investigated. The rate constant values for cyanate ion decay and EC formation are (8.0 ± 0.4) × 10(-5) and (8.9 ± 0.4) × 10(-5) s(-1), respectively, at 25 °C in 48% aqueous ethanolic solution at pH 4.5. Under the investigated experimental conditions, the rate constants are independent of the ethanol and cyanate concentrations but increase as the temperature increases (ΔH1(⧧) = 19.4 ± 1 kcal/mol, ΔS1(⧧) = −12.1 ± 1 cal/K, and ΔG1(⧧) = 23.0 ± 1 kcal/mol) and decrease as the solution pH increases. According to molecular modeling (DFT) that was performed to analyze the reaction mechanism, the isocyanic acid (HNCO) is the active EC precursor. The calculated ΔG1(⧧), ΔH1(⧧), and ΔS1(⧧) values are in very good agreement with the experimental ones.

Antitubercular activity of Ru (II) isoniazid complexes.

Despite the resistance developed by the Mycobacterium tuberculosis (MTb) strains, isoniazid (INH) has been recognized as one of the best drug for treatment of Tuberculosis (Tb). The coordination of INH to ruthenium metal centers was investigated as a strategy to enhance the activity of this drug against the sensitive and resistant strains of MTb. The complexes trans-[Ru(NH3)4(L)(INH)](2+) (L=SO2 or NH3) were isolated and their chemical and antituberculosis properties studied. The minimal inhibitory concentration (MIC) data show that [Ru(NH3)5(INH)](2+) was active in both resistant and sensitive strains, whereas free INH (non-coordinated) showed to be active only against the sensitive strain. The coordination of INH to the metal center in both [Ru(NH3)5(INH)](2+) and trans-[Ru(NH3)4(SO2)(INH)](2+) complexes led to a shift in the INH oxidation potential to less positive values compared to free INH. Despite, the ease of oxidation of INH did not lead to an increase in the in vitro INH activity against MTb, it might have provided sensitivity toward resistant strains. Furthermore, ruthenium complexes with chemical structures analogous to those described above were synthesized using the oxidation products of INH as ligands (namely, isonicotinic acid and isonicotinamide). These last compounds were not active against any strains of MTb. Moreover, according to DFT calculations the formation of the acyl radical, a proposed intermediate in the INH oxidation, is favored in the [Ru(NH3)5(INH)](2+) complex by 50.7kcalmol(-1) with respect to the free INH. This result suggests that the stabilization of the acyl radical promoted by the metal center would be a more important feature than the oxidation potential of the INH for the antituberculosis activity against resistant strains.