Theoretical Analysis of Polynuclear Zinc Complexes Isolobally Related to Hydrocarbons

Based on the isolobal analogy of ZnCp (Cp = η5-C5H5) and ZnR (R = alkyl or aryl group) fragments with hydrogen atom and fragment [Zn(CO)2] with a CH2 carbene, the following complexes [(ZnCp)2{µ-Zn(CO)2}], 1, [(ZnPh)2{µ-Zn(CO)2}], 2, [(ZnPh){µ-Zn(CO)2}(ZnCp)], 3, [(ZnCp)2{µ-Zn2(CO)4}], 4, [(ZnPh)2{µ-Zn2(CO)4}], 5, [(ZnPh){µ-Zn(CO)2}2(ZnCp)], 6, [Zn3(CO)6], 7 and [Zn5(CO)10], 8, were built. These polynuclear zinc compounds are isolobally related to simple hydrocarbons (methane, ethane, cyclopropane and cyclopentane). They have been studied by density functional theory (DFT) and quantum theory of atoms in molecules (QTAIM) to compare the nature and topology of the Zn–Zn bond with previous studies. There are bond critical points (BCPs) between each pair of adjacent Zn centers in complexes 1–8 with Zn–Zn distances within the range 2.37–2.50 Å. The nature of the Zn–Zn bond in these complexes can be described as polar rather than pure covalent bonds. Although in a subtle way, the presence of different ligands and zinc oxidation states introduces asymmetry and polarity in the Zn–Zn bond. In addition, the Zn–Zn bond is delocalized in nature in complex 7 whereas it can be described as a localized bond for the remaining zinc complexes here studied.Ministerio de Ciencia e Innovación (PGC2018-093443- B-I00 and PGC2018-099366-B-I00

Molybdenum-catalyzed enantioselective sulfoxidation controlled by a nonclassical hydrogen bond between coordinated chiral imidazolium-based dicarboxylate and peroxido ligands

Chiral alkyl aryl sulfoxides were obtained by molybdenum-catalyzed oxidation of alkyl aryl sulfides with hydrogen peroxide as oxidant in mild conditions with high yields and moderate enantioselectivities. The asymmetry is generated by the use of imidazolium-based dicarboxylic compounds, HLR. The in-situ-generated catalyst, a mixture of aqueous [Mo(O)(O2)2(H2O)n] with HLR as chirality inductors, in the presence of [PPh4]Br, was identified as the anionic binuclear complex [PPh4]{[Mo(O)(O2)2(H2O)]2( -LR)}, according to spectroscopic data and Density Functional Theory (DFT) calculations. A nonclassical hydrogen bond between one C–H bond of the alkyl R group of coordinated (LR)- and one oxygen atom of the peroxido ligand was identified as the interaction responsible for the asymmetry in the process. Additionally, the step that governs the enantioselectivity was theoretically analyzed by locating the transition states of the oxido-transfer to PhMeS of model complexes [Mo(O)(O2)2(H2O)( 1-O-LR)]- (R = H, iPr). The DDG6= is ca. 0 kcal mol-1 for R = H, racemic sulfoxide, meanwhile for chiral species the DDG6= of ca. 2 kcal mol-1 favors the formation of (R)-sulfoxide.Junta de Andalucía (Proyecto de Excelencia FQM-7079)Universidad de Sevilla (VI Plan Propio

Imido complexes of vanadium

Imido ligands have been widely used as stabilizing ligands in highoxidationstate transition metal complexes. Their chemistry has experienced a remarkable growth due to the role they play in many important reactions. Following our interest in this area, we have extended our recent results in the synthesis of bis(imido) complexes of molybdenum, d0Mo( NR)2, to the related d0 organoimido complexes of vanadium. In this contribution, we describe the synthesis and characterization of several complexes of vanadium containing the imido ligand

Oxidoperoxidomolybdenum(VI) complexes with acylpyrazolonate ligands: synthesis, structure and catalytic properties

Oxidoperoxido–molybdenum(VI) complexes containing acylpyrazolonate ligands were obtained by reaction of [Mo(O)(O)2(H2O)n] with the corresponding acylpyrazolone compounds HQR. Complexes Ph4P[Mo(O)(O2)2(QR)] (R = neopentyl, 1; perfluoroethyl, 2; hexyl, 3; phenyl, 4; naphthyl, 5; methyl, 6; cyclohexyl, 7; ethylcyclopentyl, 8) were obtained if the reaction was carried out with one equivalent of HQR in the presence of Ph4PCl. Alternatively, neutral complexes [Mo(O)(O2)(QR)2] (R = neopentyl, 9; hexyl, 10; cyclohexyl, 11) were formed when two equivalents of HQR were used in the reaction. These complexes were isolated in good yields as yellow or yellow-orange crystalline solids and were spectroscopically (IR, 1H, 13C{1H} and 31P{1H} NMR), theoretically (DFT) and structurally characterised (X-ray for 1, 2, 9 and 10). Compounds 1 and 9 were selected to investigate their catalytic behaviour in epoxidation of selected alkenes and oxidation of selected sulphides, while 10 and 11 were tested as catalyst precursors in the deoxygenation of selected epoxide substrates to alkenes, using PPh3 as the oxygen-acceptor. Complexes Ph4P[Mo(O)(O2)2(QR)] were shown to be poor catalyst precursors in oxidation reactions, while the activity of [Mo(O)(O2)(QR)2] species is good in all the studied reactions and comparable to related oxidoperoxido–molybdenum(VI) complexes. Complex [Mo(O)2(QC6)2], 12, was obtained by treatment of 10 with one equivalent of PPh3, demonstrating that the first step in the epoxide deoxygenation mechanism was the oxygen atom transfer toward the phosphane.Junta de Andalucía (Proyecto de Excelencia, FQM-7079)Universidad de Sevilla (VI Plan Propio

Preparation of the catalyst support from the oil-shale processing by-product

5-methylresorcinol and the technical mixture of oil-shale phenolic compounds were applied for carbon aerogel preparation. Gels, which were prepared via base catalyzed polymerization were dried under supercritical conditions and subsequent pyrolysis of obtained dry aerogels led to carbon aerogels. Activation of carbon aerogel with CO2 and H2O was performed and porosity and the specific surface area of activated carbon aerogels were studied. Langmuir specific surface areas of well over 2000 m2/g were achieved and microporosity of carbon aerogel samples was tuneable ranging from below 50% until over 85%. Impregnation with the complex [Pd(C4HF6O)2] was carried out in supercritical CO2 using H2 for a quick reduction of Pd(II) to Pd(0). Eventually, highly porous material decorated with nanoparticles of black palladium was obtained having a homogeneous metal distribution

Influence of N-donor bases and the solvent in oxodiperoxomolybdenum catalysed olefin epoxidation with hydrogen peroxide in ionic liquids

Biphasic catalytic olefin epoxidation systems consisting of oxodiperoxomolybdenum catalysts in 1- n -alkyl-3-methylimidazolium hexafluorophosphate ionic liquid (IL) media with aqueous hydrogen peroxide oxidant were optimised by tuning the molecular structure of the IL and employing N -heterocyclic donor base additives to inhibit hydrolysis and enhance the activity of the catalyst. The latter study was only made possible by the solubilising properties of the IL media. Of the bases investigated, pyrazoles were identified as the most efficient additive species and the best results were obtained using 3,5-dimethylpyrazole. Immobilisation of the catalyst in the IL allowed for very efficient catalyst recycling. Finally, the compound [MoO(O 2 ) 2 (3-Mepz) 2 ](3-Mepz = 3-methylpyrazole) was characterised and its structure determined by X-ray crystallography

Oil shale phenol-derived aerogels as supports for palladium nanoparticles

Palladium hexafluoroacetylacetonate [Pd(C4HF6O)2], which is both soluble and easily reducible in supercritical carbon dioxide, was used to impregnate the porous structure of carbon aerogels based on phenolic compounds from oil shale processing water. Metallic nanoparticles uniformly distributed on the surface of the carbon matrix enable it to be used as a catalyst. Through the study of various pyrolysis programs and physical activation with CO2 and H2O in the carbon aerogel preparation process, significant increases in the BET specific surface area of the carbon supports (achieving values of over 1600 m2/g) were achieved, and the possibility of tailoring the porosity of the samples (microporosity ranging from 40% up to over 90%) was realized

Synthesis, characterisation and crystal structure of a three-dimensional network of an h-bonded Ni (II) Hexametylenetetramine complex

A three-dimensional network of H-bonding nickel (II) hexamethylenetetramine complex has been synthesized and characterised and its structure determined by single crystal X-ray diffraction studies which show that [Ni(H2O)6](HMTA)2Cl32.4H2O crystallizes in the triclinic crystal system with space group PĪ, a = 9.2955(4), b = 9.3187(2), c = 9.3996 Ǻ, α = 119.4160(10), β = 94.4940(10), ɣ = 100.8680(10)º, V =682.47(4) Å3 and z = 1. The nickel atoms are each bonded to six aquo ligands giving an octahedral geometry. The ligand hexamethylenetetramine (HMTA) and chloride ions are bonded to water molecules through hydrogen bonding. Thermal studies show a decomposition pattern corresponding to the loss of the coordinated and uncoordinated water molecules, chloride ions and HMTA ligand in the form of a mixture of gases

Association Between Preexisting Versus Newly Identified Atrial Fibrillation and Outcomes of Patients With Acute Pulmonary Embolism

Background Atrial fibrillation (AF) may exist before or occur early in the course of pulmonary embolism (PE). We determined the PE outcomes based on the presence and timing of AF. Methods and Results Using the data from a multicenter PE registry, we identified 3 groups: (1) those with preexisting AF, (2) patients with new AF within 2 days from acute PE (incident AF), and (3) patients without AF. We assessed the 90-day and 1-year risk of mortality and stroke in patients with AF, compared with those without AF (reference group). Among 16 497 patients with PE, 792 had preexisting AF. These patients had increased odds of 90-day all-cause (odds ratio [OR], 2.81; 95% CI, 2.33-3.38) and PE-related mortality (OR, 2.38; 95% CI, 1.37-4.14) and increased 1-year hazard for ischemic stroke (hazard ratio, 5.48; 95% CI, 3.10-9.69) compared with those without AF. After multivariable adjustment, preexisting AF was associated with significantly increased odds of all-cause mortality (OR, 1.91; 95% CI, 1.57-2.32) but not PE-related mortality (OR, 1.50; 95% CI, 0.85-2.66). Among 16 497 patients with PE, 445 developed new incident AF within 2 days of acute PE. Incident AF was associated with increased odds of 90-day all-cause (OR, 2.28; 95% CI, 1.75-2.97) and PE-related (OR, 3.64; 95% CI, 2.01-6.59) mortality but not stroke. Findings were similar in multivariable analyses. Conclusions In patients with acute symptomatic PE, both preexisting AF and incident AF predict adverse clinical outcomes. The type of adverse outcomes may differ depending on the timing of AF onset.info:eu-repo/semantics/publishedVersio