Molecular Organometallic Chemistry on Surfaces: Reactivity of Metal Carbonyls on Metal Oxides

Metal carbonyls react on metal oxide surfaces to give a wide range of structures analogous to those of known compounds. The reactions leading to formation of surface-bound metal carbonyls are explained by known molecular organometallic chemistry and the functional group chemistry of the surfaces. The reaction classes include formation of acid-base adducts as the oxygen of a carbonyl group donates an electron pair to a Lewis acidic center; nucleophilic attack at CO ligands by basic surface hydroxyl groups or O^2? ions; ion-pair formation by deprotonation of hydrido carbonyls to give carbonylate ions; interaction of bifunctional complexes with surface acid-base pair sites such as [Mg^2⊕O^2?]; and oxidative addition of surface hydroxyl groups to metal clusters. The reactions of surface-bound organometallic species include redox condensation and cluster formation on basic surfaces (paralleling the reactions in basic solution) as well as oxidation of mononuclear metal complexes and oxidative fragmentation of metal clusters by reaction with surface hydroxyl groups. Most supported metal carbonyls are unstable at high temperatures, but some, including osmium carbonyl cluster anions on the basic MgO surface, are strongly stabilized in the presence of CO and are precursors of catalysts for CO hydrogenation at 550 K.     

UV laser synthesis of nanoparticles in the gas phase

This review deals with the UV laser photodissociation of metal carbonyls, ferrocene, carbon suboxide, and other precursors. The formation of supersaturated atomic vapors followed by the formation of carbon, metal, and metal–carbon nanoparticles is discussed. Application of UV laser synthesis to preparation of catalytic nanomaterials is considered.     

Nanodispersed metal and metal oxide particles in polymeric matrices from polyacrylonitrile precursors

Two ways of the colloid formation of metals and metal oxides in the polyacrylonitrile (PAN) and its copolymer (1.5 wt % of itaconic acid) (PAN-I) have been studied. The thermal decomposition of W, Mo and Cr carbonyl complexes with PAN, prepared by the interaction of PAN nitrile groups with VI B group metal hexacarbonyls has been investigated. The thermolysis under air leads to a formation of metal oxide particles. For the Cr-containing PAN, the presence of dispersed Cr₂O₃ with a size less than 3 nm was estimated by ESR. Co-containing polymers were prepared by mixing Co₂(CO)₈ with PAN-I in DMF. It was found that Co₂(CO)₈ interacts with DMF giving salt [Co(DMF)₆]²⁺[Co(CO)₄]-₂. By ferromagnetic resonance and SAXS, colloid size depends on thermolysis conditions and loading of the Co complex and varies from 1 to 10 nm.     

Solvent extraction kinetics of rare earth elements

The kinetics of solid-liquid extraction of rare earth elements (RE) (La, Ce, Sm, Dy and Yb) were studied with 1-(2-pyridylazo)-2-naphthol (PAN) at 60 degrees C using paraffin wax as a diluent. The rate of extraction is first order with respect to metal ion and hydrogen ion in the aqueous phase and second order with respect to the extractant in the organic phase. The rate-determining step is the formation of an [RE(PAN)(2)](+) complex between RE(3+) and PAN in the aqueous phase. The rate constant for the extraction was found to be about 10(11) 1 mol(-1) s(-1). The temperature dependence of extraction rate was determined and the activation parameters were calculated.     

Small molecules control the formation of Pt nanocrystals: a key role of carbon monoxide in the synthesis of Pt nanocubes

In many previous studies, nonaqueous synthesis of Pt nanocubes with tunable size has been achieved by the use of metal carbonyls (e.g., Fe(CO)(5), Co(2)(CO)(8), W(CO)(6)). The presence of zero-valent metals in the carbonyls was demonstrated as the key factor to the nanocube formation but the role of CO was entirely ignored. By using CO alone, we have now demonstrated that the favorable growth of Pt nanocubes in the presence of CO is mainly owing to the effect that the Pt (100) surface is stabilized by the co-adsorption of CO and amine.     

Zur Kenntnis der sogenannten «Erdalkalicarbonyle»

The alkaline earth metals in liquid ammonia react with carbon monoxide to form the so-called ‘alkaline earth metal carbonyls’. These products which according to older literature are formulated as M(CO)₂(M = Ca, Sr, Ba) contain only 65–70% of the expected amount of carbon monoxide. As can be seen from the nitrogen content of the compounds the solvent ammonia participates in the reaction. By hydrolysis leading to a variety of compounds it is demonstrated that the ‘alkaline earth metal carbonyls’ are mixtures of substances such as metal acetylenediolates, metal methoxides, and ammonium carbonate. These mixtures are different from the ‘alkali carbonyls’ as for instance can be seen from the low acetylenediolate content of the ‘alkaline earth metal carbonyls’.     

The synthesis of organotin-transition metal carbonyl complexes from tris(trimethylstannyl)amine and hexamethyldistannoxane

Trimethyltin derivatives of metal carbonyls containing SnMn, SnMo, SnFe, SnCo and SnNi bonds have been obtained by the action of metal-metal bonded dimeric metal carbonyls with tris(trimethylstannyl)amine or hexamethyldistannoxane.     

Low-coordinate transition-metal complexes of a carbon-substituted hemiporphyrazine

The metallation of the core-modified phthalocyanine analogue dicarbahemiporphyrazine with manganese, iron, and cobalt results in the formation of low-coordinate metal(II) complexes. All three compounds are produced by the reaction of metal carbonyls with the free base macrocycle. As in many other carbaporphyrinoids, the internal C-H bonds remain intact upon metallation, resulting in the formation of two long-range agostic-type interactions. Each metal can thus be considered as a three-coordinate ion, where two inner isoindolene nitrogens and a single axial pyridine are bound to the metal. The manganese and cobalt complexes, Mn(dchp)py and Co(dchp)py, are nearly isostructural, but the iron complex, Fe(dchpH2)py, exhibits a reduction at an iminic double bond upon metallation.     

Experimental and theoretical evidence for the formation of zinc tricarbonyl in solid argon

Zinc carbonyls are extremely rare. Here we report experimental and theoretical evidence of unprecedented zinc tricarbonyl, Zn(CO)3, the next member of the series of 18-electron metal carbonyls Cr(CO)6 --> Fe(CO)5 --> Ni(CO)4, whereas there is no evidence for the formation of the zinc mono- and dicarbonyls Zn(CO)n (n = 1, 2). DFT calculations predict that the Zn(CO)3 molecule has a singlet ground state with D3h symmetry. The formation of Zn(CO)3 involves 4s --> 4p promotion of the Zn atom, which increases the Zn-CO bonding by decreasing the sigma repulsion and significantly increasing the Zn 4sp hybrid orbitals --> CO pi* back-donation.     

Detection of free nickel monocarbonyl, NiCO: rotational spectrum and structure

Unsaturated transition metal carbonyls are important in processes such as organometallic synthesis, homogeneous catalysis, and photochemical decomposition of organometallics. In particular, a metal monocarbonyl offers a zeroth-order model for interpreting the chemisorption of a CO molecule on a metal surface in catalytic activation processes. Quite large numbers of theoretical papers have appeared which predict spectroscopic and structural properties of transition metal carbonyls. The nickel monocarbonyl NiCO has been one of the metal carbonyls most extensively studied by the theoretical calculations. At least 50 theoretical studies have been published on this simplest transition metal carbonyl up to the present time. However, experimental evidence of NiCO is much more sparse than theoretical predictions, and the actual structure of NiCO has never been determined by any experimental methods. This Communication reports the first preparation of free nickel monocarbonyl and observation of its rotational transitions. The NiCO molecule was generated by the sputtering reaction of a Ni cathode in the presence of CO. The accurate bond lengths of Ni-C and C-O were experimentally determined from isotopic data and were compared with the theoretical predictions for the first time.     

Die übergangsmetall-katalysierte reduktive Carbonylierung von Arylaziden zu 1,3-Diarylharnstoffen

Several group VIII metal carbonyls catalyze decomposition of aryl azides to yield in the presence of carbon monoxide and a low concentration of hydrogen the corresponding symmetrical disubstituted ureas. Based on the formation of nitrenoid intermediates, probable and alternative reaction mechanism pathways have been examined.     

Preparation of amidoxime-modified polyacrylonitrile (PAN-oxime) nanofibers and their applications to metal ions adsorption

Polyacrylonitrile (PAN) nanofibers were applied to metal adsorption. PAN nanofibers (prepared by an electrospinning technique) were chemically modified with amidoxime groups, which are suitable for metal adsorption due to their high adsorption affinity for metal ions. The adsorption of the amidoxime-modified PAN (PAN-oxime) (25% conversion) nanofibers followed Langmuir isotherm. The saturation adsorption capacities for Cu(II) and Pb(II) of 52.70 and 263.45 mg/g (0.83 and 1.27 mmol/g), respectively, indicating that the monolayer adsorption occurred on the nanofiber mats. In addition, over 90% of metals were recovered from the metal-loaded PAN-oxime nanofibers in a 1 mol/L HNO₃ solution after 1 h.     

The application of the simplified form of the quasiequilibrium theory to the mass spectra of some mononuclear metal carbonyls

The concept of molecular ions and metal-containing fragment ions formed in the mass spectra of the mononuclear metal carbonyls, M(CO)₆ (M = Cr, Mo,W), Fe(CO)₅, Ni(CO)₄, containing the metal in an excited state appears to violate the quasi-equilibrium theory. Calculations, using the simplified form of the theory, show that the high values obtained for the heats of formation of the metal ions determined by mass spectrometry axe consistent with the “excess energies” representing kinetic shifts.     

Phosphorylated polyacrylonitrile‐based electrospun nanofibers for removal of heavy metal ions from aqueous solution

The phosphorylated polyacrylonitrile‐based (P‐PAN) nanofibers were prepared by electrospinning technique and used for removal of Cu²⁺, Ni²⁺, Cd²⁺, and Ag⁺ from aqueous solution. The morphological and structural properties of P‐PAN nanofibers were characterized by scanning electron microscope and Fourie transform infrared spectra. The P‐PAN nanofibers were evaluated for the adsorption capacity at various pH, contact time, and reaction temperature in a batch system. The reusability of P‐PAN nanofibers for the removal of heavy metal ions was also determined. Adsorption isotherms and adsorption kinetics were also used to examine the fundamental adsorption properties. It is found that the P‐PAN nanofibers show high efficiency, and the maximal adsorption capacities of metal ions as calculated from the Langmuir model were 92.1, 68.3, 14.8, and 51.7 mg/g, respectively. The kinetics of the heavy metal ions adsorption were found to follow pseudo‐second‐order rate equation, suggesting chemical adsorption can be regarded as the major factor in the adsorption process. Sorption/desorption results reveal that the obtained P‐PAN nanofibers can remain high removal efficiency after four cycles.     

Addition of alkyl radicals to transition-metal-coordinated CO: calculation of the reaction of [Ru(CO)5] and related complexes and relevance to alkane carbonylation

Electronic structure methods have been used to study the transition state and products of the reaction between alkyl radicals and CO coordinated in transition-metal complexes. At the B3LYP DFT level, methyl addition to a carbonyl of [Ru(CO)5] or [Ru(CO)3(dmpe)] is calculated to be about 6 kcal/mol more exothermic than addition to free CO. In contrast, methyl addition to [Mo(CO)6] is 12 kcal/mol less exothermic than addition to CO, while the reaction enthalpy of methyl addition to [Pd(CO)4] is comparable to that of free CO. Related results are obtained at the CCSD-T level and for the reactions of the cyclohexyl radical. The transition state for these reactions is characterized by significant distortion of the geometry of the reactant complex, which include lengthening and bending of the M-CO bond, but with negligible C-C bond formation. Accordingly, the activation energy for addition to coordinated carbonyls is 2-10 kcal/mol greater than that of addition to free CO. Additional calculations were also carried out on representative unsaturated metal carbonyls. The calculated results afford an understanding of the mechanism of previously reported photochemical alkane carbonylation systems utilizing d(8)-ML5 metal carbonyls as cocatalysts. In particular, it is strongly indicated that such systems operate via direct attack by an alkyl radical at a CO ligand, a reaction that has not previously been proposed.     

Column chromatographic separation of metal ions on 1-(2-pyridylazo)-2-napthol modified amberlite IR-120 resin

Cation exchange resin, Amberlite IR-120, has been modified by the sorption of 1-(2-pyridylazo)-2-napthol (PAN) at pH 6.0. The optimum conditions for the sorption of PAN on the resin have been established. The maximum sorption of PAN was found to be 8.70 micromol/g. In order to explore the separation possibilities of the material, distribution coefficients of a number of metal ions were determined in various solvent systems. A number of binary separations of metal ions of analytical interest have been carried out using columns packed with this material. In order to demonstrate the practical utility of this material, Zn2+ and Hg2+ have been selectively separated from synthetic mixtures of metal ions and assay of Zn2+ and Fe2+ in commercially available pharmaceutical tablets; namely Fesofor-Z and FE-Z, was carried out.     

Studies on the synergetic effect of group viii transition metal carbonyls on homogeneous catalysis of the water-gas shift reaction

Homogeneous catalysis of the water-gas shift reaction by Group VIII mixed metal carbonyls and by mixtures of Group VIII metal carbonyls in pyridine solution was examined under mild conditions (T= 100°C, P_co = 0.42–0.60 atm).A weak synergetic effect of Group VIII metals was observed between iron and iridium carbonyls. A stronger synergetic behaviour of mixed metal Fe/Ru catalyst precursors (Fe₂Ru(CO)₁₂ and FeRu₂(CO)₁₂) was noted. The effect of phosphine and phosphite substitution on Fe₂Ru(CO)₁₂ and FeRu₂(CO)₁₂ was examined. Only monosubstitution on Fe₂Ru(CO)₁₂ was found to have an enhancing effect on catalytic activity.Rhodium carbonyls, which were found to produce the most active catalyst solution under homogeneous water-gas shift conditions, did not show a synergetic behaviour with other Group VIII metals.     

Selective Activation of Aromatic Aldehydes Promoted by Dispersion Interactions: Steric and Electronic Factors of a π-Pocket within Cage-Shaped Borates for Molecular Recognition

Selective bond formations are one of the most important reactions in organic synthesis. In the Lewis acid mediated electrophile reactions of carbonyls, the selective formation of a carbonyl–acid complex plays a critical role in determining selectivity, which is based on the difference in the coordinative interaction between the carbonyl and Lewis acid center. Although this strategy has attained progress in selective bond formations, the discrimination between similarly sized aromatic and aliphatic carbonyls that have no functional anchors to strongly interact with the metal center still remains a challenging issue. Herein, this work focuses on molecular recognition driven by dispersion interactions within some aromatic moieties. A Lewis acid catalyst with a π-space cavity, which is referred to as a π-pocket, as the recognition site for aromatic carbonyls is designed. Cage-shaped borates 1 B with various π-pockets demonstrated significant chemoselectivity for aromatic aldehydes 3 b – f over that of aliphatic 3 a in competitive hetero-Diels–Alder reactions. The effectiveness of our catalysts was also evidenced by intramolecular recognition of the aromatic carbonyl within a dicarbonyl substrate. Mechanistic and theoretical studies demonstrated that the selective activation of aromatic substrates was driven by the preorganization step with a larger dispersion interaction, rather than the rate-determining step of the C−C bond formation, and this was likely to contribute to the preferred activation of aromatic substrates over that of aliphatic ones.     

A Robust Analytical Approach for the Identification of Specific Protein Carbonylation Sites: Metal-Catalyzed Oxidations of Human Serum Albumin

The formation of protein carbonyls in the metal-catalyzed oxidation of human serum albumin (HSA) is characterized using a new analytical approach that involves tagging the modification site with multiple hydrazide reagents. Protein carbonyl formation at lysine and arginine residues was catalyzed with copper and iron ions, and the resulting oxidation patterns in HSA are contrasted. A total of 18 modification sites were identified with iron-ion catalysis and 14 with copper-ion catalysis. However, with the more stringent requirement of identification with at least two tagging reagents, the number of validated modification sites drops to 10 for iron and nine for copper. Of the 14 total validated sites, there were only five in common for the two metal ions. The results illustrate the value of using multiple tagging agents and highlight the selective and specific nature of metal-catalyzed protein oxidations.     

Naked metal nanoparticles from metal carbonyls in ionic liquids: Easy synthesis and stabilization

An overview with more than 160 references on the synthesis and stabilization of metal nanoparticles (M-NPs) from metal carbonyls, metal salts in ionic liquids (ILs) and in particular from metal carbonyls in ionic liquids is given. The synthesis of M-NPs can proceed by chemical reduction, thermolysis, photochemical decomposition, electroreduction, microwave and sonochemical irradiation. Commercially available metal carbonyls M_x(CO)_y are elegant precursors as they contain the metal atoms already in the zero-valent oxidation state needed for M-NPs. No extra reducing agent is necessary. The side product CO is largely given off to the gas phase and removed from the dispersion. The microwave induced thermal decomposition of metal carbonyls M_x(CO)_y in ILs provides an especially rapid and energy-saving access to M-NPs because of the ILs significant absorption efficiency for microwave energy due to their high ionic charge, high polarity and high dielectric constant. The electrostatic and steric properties of ionic liquids allow for the stabilization of M-NPs without the need of additional stabilizers, surfactants or capping ligands and are highlighted by pointing to the DLVO (Derjaugin–Landau–Verwey–Overbeek) and extra-DLVO theory. Examples for the direct use of M-NP/IL dispersions in hydrogenation catalysis of cyclohexene and benzene are given.