On-Surface Synthesis of Porous Carbon Nanoribbons on Silver: Reaction Kinetics and the Influence of the Surface Structure

We report on the influence of the surface structure and the reaction kinetics in the bottom-up fabrication of porous nanoribbons on silver surfaces using low-temperature scanning tunneling microscopy. The porous carbon nanoribbons are fabricated by the polymerization of 1,3,5-tris(3-bromophenyl)benzene directly on the Ag surface using an Ullmann-type reaction in combination with dehydrogenative coupling reactions. We demonstrate the successful on-surface synthesis of porous nanoribbons on Ag(111) and Ag(100) even though the self-assemblies of the intermediate organometallic structures and covalently-linked polymer chains are different on both surfaces. Furthermore, we present the formation of isolated porous nanoribbons by kinetic control. Our results give valuable insights into the role of substrate-induced templating effects and the reaction kinetics in the on-surface synthesis of conformationally flexible molecules.     

Five-membered metallacycles of titanium and zirconium--attractive compounds for organometallic chemistry and catalysis

In these days a renaissance of metallacycles as an increasingly important class of organometallic compounds for synthetic and catalytic applications is evident, making such very attractive for a plethora of investigations. Titanocene and zirconocene bis(trimethylsilyl)acetylene complexes, regarded as three-membered metallacycles (1-metallacyclopropenes), present a rich chemistry towards unsaturated molecules. By elimination of the alkyne these complexes form by reaction with unsaturated compounds five-membered titana- and zirconacycles, all of which are relevant to stoichiometric and catalytic C-C coupling and cleavage reactions of unsaturated molecules.     

Identification and hydrogenation of C2 on Pt(111)

Reflection absorption infrared spectroscopy (RAIRS) and temperature-programmed desorption (TPD) were used to identify the molecular species formed upon the reaction of hydrogen with surface carbon that is deposited by exposing acetylene to a Pt(111) surface held at 750 K. At this temperature, the acetylene is completely dehydrogenated and all hydrogen is desorbed from the surface. Upon subsequent hydrogen exposure at 85 K followed by sequential annealing to higher temperatures, ethylidyne (CCH3), ethynyl (CCH), and methylidyne (CH) are formed. The observation of these species indicates that carbon atoms and C2 molecules exist as stable species on the surface over a wide range of temperatures. Through a combination of RAIRS intensities, hydrogen TPD peak areas, and Auger electron spectroscopy, quantitative estimates of the coverages of the various species were obtained. It was found that 79% of the acetylene-derived carbon was in the form of C2 molecules, with the remainder in the form of carbon atoms. Essentially all of the acetylene-derived carbon could be hydrogenated. In contrast, 85% of an equivalent coverage of carbon deposited by ethylene exposure at 750 K was found to be inert toward hydrogenation.     

Correlating electronic properties of bimetallic surfaces with reaction pathways of C2 hydrocarbons

The rate and selectivity of chemical reactions on transition-metal surfaces can be controlled by using different bimetallic combinations. The interaction of bimetallic components leads to a change in the electronic properties of the surface, which in turn produces a change in chemical reactivity. In the current paper, we illustrate the correlation of the electronic properties of bimetallic surfaces with the reaction pathways of C2 hydrocarbons. Density functional theory (DFT) was used to study the binding of hydrogen, ethylene, acetylene, ethyl, and vinyl on monometallic and bimetallic transition-metal surfaces. The binding energies of these species were found to correlate with the d-band centers of these surfaces. The binding energies for hydrogen atoms on bimetallic surfaces were lower than for those on the corresponding parent metal surfaces. This trend was consistent for ethylene and acetylene binding. Comparative studies between acetylene and ethylene revealed that acetylene was more strongly bonded to the monometallic and the bimetallic surfaces than was ethylene. Bond order conservation (BOC) theory was used to calculate the activation barriers for ethyl dehydrogenation to ethylene and vinyl dehydrogenation to acetylene. The activation barriers for these reactions were correlated with the surface d-band center of the substrates.     

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.     

Laser photochemistry of organometallic compounds related to applications in microelectronics

Photochemistry of organometallic compounds achieves a marriage of a rich variety of organometallic chemistry and the full potential of electronically excited states of molecules. The application of lasers as light sources adds a great many new features to these studies, which cannot be attained by other means, because lasers provide light of such a high quality, e.g. a high-intensity, energetic (i.e. wavelength) purity, a high degree of coherence, and a high spatial and temporal resolution. Laser photochemistry of organometallic compounds, such as laser photochemical vapor deposition (LPCVD), laser ablation, and photochemical dry etching, forms the basis of many important industrial processes which sustain the present-day microelectronics industries. Lasers are used not only to photodissociate organometallic molecules, but to monitor the reaction steps by probing the starting material, chemical intermediate, or final product by many laser-based spectroscopic methods. Although it is a very young area of science (the first laser was operated in 1960), this research area is now really ebullient, as a result of strong interest from both the fundamental and the practical sides. Laser photochemistry of organometallic compounds extends a wide and fertile research frontier, full of challenge and novel possibilities. In the present review, the present status of laser (ultraviolet and visible) photochemistry of organometallic compounds related to these industrial applications is briefly reviewed, with special emphasis on the basic studies of the relevant photochemistry and their relationship to photochemical processes on solid surfaces.     

Acrylate formation via metal-assisted C-C coupling between CO2 and C2H4: reaction mechanism as revealed from density functional calculations

The reaction path for the formation of a binuclear hydrido-acrylate complex in a CO(2)-C(2)H(4) coupling process is explored in detail by locating the key intermediates and transition states on model potential energy surfaces derived from density functional calculations on realistic models. The formation of the new C-C bond is shown to take place via oxidative coupling of coordinated CO(2) and C(2)H(4) ligands resulting in a metalla-lactone intermediate, which can rearrange to an agostic species allowing for a beta-hydrogen shift process. The overall reaction is predicted to be clearly exothermic with all intermediates lying below the reactants in energy, and the highest barrier steps correspond to C-C coupling and beta-hydrogen transfer. The phosphine ligands are found to play an important role in various phases of the reaction as their dissociation controls the coordination of CO(2), the formation of the agostic intermediate, and the dimerization process; furthermore, their presence facilitates the oxidative coupling by supplying electrons to the metal center. Our results provide a theoretical support for the reaction mechanism proposed from experimental observations. The effect of the solvent medium on the relative energy of reaction intermediates and transition states is examined and found important in order to predict reliable energetics.     

Triplet organometallic reactivity under ambient conditions: an ultrafast UV pump/IR probe study.

The reactivity of triplet 16-electron organometallic species has been studied in room-temperature solution using femtosecond UV pump IR probe spectroscopy. Specifically, the Si-H bond-activation reaction of photogenerated triplet Fe(CO)(4) and triplet CpCo(CO) with triethylsilane has been characterized and compared to the known singlet species CpRh(CO). The intermediates observed were studied using density functional theory (DFT) as well as ab initio quantum chemical calculations. The triplet organometallics have a greater overall reactivity than singlet species due to a change in the Si-H activation mechanism, which is due to the fact that triplet intermediates coordinate weakly at best with the ethyl groups of triethylsilane. Consequently, the triplet species do not become trapped in alkyl-solvated intermediate states. The experimental results are compared to the theoretical calculations, which qualitatively reproduce the trends in the data.     

Low-temperature synthesis of amorphous carbon nanocoils via acetylene coupling on copper nanocrystal surfaces at 468 K: a reaction mechanism analysis

A new type of amorphous helical carbon nanofibers has been synthesized using copper nanocatalysts and an acetylene gas source at atmospheric pressure. The nanofibers are grown at 468 K, which is the lowest temperature by ordinary metal-catalyzed thermal chemical vapor deposition of hydrocarbon, and exhibit a symmetric growth mode in the form of twin helices. IR, XRD, Raman, and C/H molar ratio analyses reveal a polymer-like structure with a weak trans-polyacetylene feature. The nanofibers are a mixture of solid polymers and a small amount of carbon. A reaction mechanism has been proposed on the basis of the previous studies of acetylene adsorption, desorption properties, and surface reactions on copper (111), (110), and (001) planes under ultrahigh-vacuum (UHV) conditions as well as the results obtained in our study. The reaction mechanism of acetylene on copper single-crystal surfaces under UHV conditions indeed reflects the reaction mechanism under practical catalytic conditions at atmospheric pressure. The nanofibers grow mainly via acetylene coupling to solid polymers on copper nanocrystal surfaces. Acetylene also couples to yield small amounts of liquid oligomers and gaseous products, and undergoes slight carbon deposition during the fiber growth.     

Competition between H and CO for Active Sites Governs Copper‐Mediated Electrosynthesis of Hydrocarbon Fuels

The dynamics of carbon monoxide on Cu surfaces was investigated during CO reduction, providing insight into the mechanism leading to the formation of hydrogen, methane, and ethylene, the three key products in the electrochemical reduction of CO₂. Reaction order experiments were conducted at low temperature in an ethanol medium affording high solubility and surface‐affinity for carbon monoxide. Surprisingly, the methane production rate is suppressed by increasing the pressure of CO, whereas ethylene production remains largely unaffected. The data show that CH₄ and H₂ production are linked through a common H intermediate and that methane is formed through reactions among adsorbed H and CO, which are in direct competition with each other for surface sites. The data exclude the participation of solution species in rate‐limiting steps, highlighting the importance of increasing surface recombination rates for efficient fuel synthesis.     

Electrochemical functionalization of carbon surfaces by aromatic azide or alkyne molecules: a versatile platform for click chemistry

The electrochemical reduction of phenylazide or phenylacetylene diazonium salts leads to the grafting of azido or ethynyl groups onto the surface of carbon electrodes. In the presence of copper(I) catalyst, these azide- or alkyne-modified surfaces react efficiently and rapidly with compounds bearing an acetylene or azide function, thus forming a covalent 1,2,3-triazole linkage by means of click chemistry. This was illustrated with the surface coupling of ferrocenes functionalized with an ethynyl or azido group and the biomolecule biotin terminated by an acetylene group.     

Stoichiometric and catalytic reactivity of organometallic fragments supported on inorganic oxides

The reaction of some organometallic complexes with the surfaces of inorganic oxides leads to the formation of surface organometallic complexes, chemically bound to the surface yet retaining many features of their molecular structure. These surface organometallic complexes can therefore be considered to belong to both the molecular and solid states. In cases where such complexes have been structurally characterised, their reactivity can be interpreted with molecular concepts. In this review article, the stoichiometric and catalytic reactivity of some relatively well-defined surface organometallic fragments is surveyed. Many elementary steps which have precedent in molecular organometallic chemistry and homogeneous catalysis have now been demonstrated with surface organometallic fragments, including reversible ligand binding, oxidative addition, reductive elimination, protonation, heterolytic metal—carbon bond cleavage, electrophilic CH bond activation and insertion into metal—carbon bonds. In some cases, the supported organometallic complexes are highly effective low temperature catalysts, a phenomenon which is not always observed with molecular analogues nor with conventionally prepared heterogeneous catalysts. Applications of surface organometallic chemistry to catalytic alkane hydrogenolysis, olefin isomerisation and hydrogenation, the Fischer—Tropsch synthesis and the water—gas shift reaction are discussed. Proposed mechanisms for several representative catalytic cycles are presented.     

Molecular approach to the study of the mechanisms of alkyl reactions on metal surfaces

The surface chemistry of alkyl species adsorbed on solid transition metal surfaces is contrasted here against the behavior of analog organometallic systems. The several methods developed in recent years for the clean production of alkyl surface moieties on well characterized metal surfaces are described, and the main decomposition pathways observed after thermal activation of those alkyl species, namely, elimination of both hydride and methyl groups from either the alpha or the beta position, reductive elimination processes related to hydrogenation and to carbon—carbon coupling steps, and insertion, homolysis, and displacement reactions, are discussed. A brief outlook on the future of this field is presented.     

Steering Surface Reaction Dynamics with a Self‐Assembly Strategy: Ullmann Coupling on Metal Surfaces

Ullmann coupling of 4‐bromobiphenyl thermally catalyzed on Ag(111), Cu(111), and Cu(100) surfaces was scrutinized by scanning tunneling microscopy as well as theoretical calculations. Detailed experimental evidence showed that initial formation of organometallic intermediates on the surface, as self‐assembled structures or sparsely dispersed species, is determined by the subsequent reaction pathway. Specifically, the assembled organometallic intermediates at full coverage underwent a single‐barrier process to directly convert into the final coupling products, while the sparsely dispersed intermediates at low coverage went through a double‐barrier process via newly identified clover‐shaped intermediates prior to formation of the final coupling products. These findings demonstrate that a self‐assembly strategy can efficiently steer surface reaction pathways and dynamics.     

Adsorption of NO and CO and specific features of their interaction on the Pt(100) surface

This article presents an analytical review of the author’s results and the literature concerning the nature of species resulting from NO and CO adsorption on the unreconstructed (1 × 1) and reconstructed hexagonal (hex) Pt(100) surfaces, including specific features of the reactions between these species. At 300 K, both surfaces adsorb NO and CO mainly in their molecular states. When adsorbed on Pt(100)-1 × 1, the NO_ads and CO_ads molecules are uniformly distributed on the surface. Under the same conditions, the hexagonal surface undergoes adsorption-induced reconstruction with the formation of NO_ads/1 × 1 and CO_ads/1 × 1 islands, which are areas of the unreconstructed phase saturated with adsorbed molecules and surrounded with the adsorbate-free hex phase. In adsorption on structurally heterogeneous surfaces containing both hex and 1 × 1 areas, the 1 × 1 and hex phases are occupied in succession, the latter undergoing reconstruction into the 1 × 1 phase. The reaction between NO and CO on the unreconstructed surfaces occurs even at room temperature and results in the formation of N₂ and CO₂ in quantitative yield. On the hexagonal surface, a stable layer of adsorbed molecules as (NO_ads + CO_ads)/1 × 1 mixed islands forms under these conditions. Above 350 K, the reaction in the mixed islands is initiated by the desorption of small amounts of the initial compounds, and this is followed by rapid self-acceleration leading to a surface explosion yielding N₂, CO₂, and N₂O (minor product). These products show themselves as very narrow desorption peaks in the temperature-programmed reaction spectrum.     

Reactivity of C1 surface species formed in methane activation on Zn-modified H-ZSM-5 zeolite

Solid-state (13)C magic angle spinning (MAS) NMR spectroscopy investigations identified zinc methyl species, formate species, and methoxy species as C(1) surface species formed in methane activation on the zeolite Zn/H-ZSM-5 catalyst at T≤573 K. These C(1) surface species, which are possible intermediates in further transformations of methane, were prepared separately by adsorption of (13)C-enriched methane, carbon monoxide, and methanol onto zinc-containing catalysts, respectively. Successful isolation of each surface species allowed convenient investigations into their chemical nature on the working catalyst by solid-state (13)C MAS NMR spectroscopy. The reactivity of zinc methyl species with diverse probe molecules (i.e., water, methanol, hydrochloride, oxygen, or carbon dioxide) is correlated with that of organozinc compounds in organometallic chemistry. Moreover, surface formate and surface methoxy species possess distinct reactivity towards water, hydrochloride, ammonia, or hydrogen as probe molecules. To explain these and other observations, we propose that the C(1) surface species interconvert on zeolite Zn/H-ZSM-5. As implied by the reactivity information, potential applications of methane co-conversion on zinc-containing zeolites might, therefore, be possible by further transformation of these C(1) surface species with rationally designed co-reactants (i.e., probe molecules) under optimized reaction conditions.     

In situ soft X-ray studies of ethylene oxidation mechanisms and intermediates on the Pt(111) surface

In situ studies of ethylene oxidation on Pt(111) have been performed using a powerful combination of fluorescence yield soft X-ray methods for temperatures up to 600 K and oxygen pressures up to 0.01 Torr. Absolute carbon coverages have been determined both in steady-state and dynamic catalytic conditions on the Pt(111) surface. Fluorescence yield near-edge spectroscopy (FYNES) and temperature-programmed fluorescence yield near-edge spectroscopy (TP-FYNES) experiments above the carbon K edge were used to identify the structure and bonding of the dominant surface species during oxidation. TP-FYNES experiments of preadsorbed ethylene coverages in oxygen pressures up to 0.01 Torr indicate a stable intermediate is formed over the 215-300 K temperature range. By comparing the intensity of the C-H sigma resonance at the magic angle with the intensity in the carbon continuum, the stoichiometry of this intermediate has been determined explicitly. Based on calibration with known C-H stoichiometries, the intermediate has a C(2)H(3) stoichiometry for oxygen pressures up to 0.01 Torr, indicating oxydehydrogenation occurs before skeletal oxidation. FYNES spectra at normal and glancing incidences were performed to characterize the structure and bonding of this intermediate. Using FYNES spectra of ethylene, ethylidyne, and acetylene as reference standard, this procedure indicates the oxidation intermediate is tri-sigma vinyl. Thus, oxidation of ethylene proceeds through a vinyl intermediate, with oxydehydrogenation preceding skeletal oxidation.     

NO and dichloroethene reactivity on single crystal and supported Cu nanoparticles: just how big is the materials gap?

Infrared and molecular beam experiments are used to compare and contrast the adsorption and reaction of NO and trans-1,2-dichloroethene on Cu(110) and on Cu nanoclusters deposited on a 5 A thick Al(2)O(3) film. The overall reaction of NO, leading to decomposition, is almost identical in the two systems, with both types of Cu surfaces promoting the formation of NO dimers, which are precursors to the dissociation products N(2)O, N(2) and O. Although the overall reaction is independent of surface structure, the IR spectra clearly show differences in the adsorption sites occupied on the single crystal and the clusters, a disparity that is also shown by CO adsorption experiments. In contrast, the reaction pathway of dichloroethene does show differences on the two types of Cu surfaces. On both surfaces, the initial reaction step is insensitive to structure and efficient dechlorination leads to the production of adsorbed acetylene. However, the fate of this intermediate depends critically on the underlying surface. On Cu(110), the acetylene trimerises readily into benzene at 350 K. However, this reaction shows a significant size dependent behaviour on the supported nanocluster systems, with the probability for trimerisation diminishing with decreasing cluster size.     

Bonding character of intermediates in on-surface Ullmann reactions revealed with energy decomposition analysis

On-surface synthesis has become a thriving topic in surface science. The Ullmann coupling reaction is the most applied synthetic route today, but the nature of the organometallic intermediate is still under discussion. We investigate the bonding nature of prototypical intermediate species (phenyl, naphthyl, anthracenyl, phenanthryl, and triphenylenyl) on the Cu(111) surface with a combination of plane wave and atomic orbital basis set methods using density functional theory calculations with periodic boundary conditions. The surface bonding is shown to be of covalent nature with a polarized shared-electron bond supported by π-back donation effects using energy decomposition analysis for extended systems (pEDA). The bond angle of the intermediates is determined by balancing dispersion attraction and Pauli repulsion between adsorbate and surface. The latter can be significantly reduced by adatoms on the surface. We furthermore investigate how to choose computational parameters for pEDA of organic adsorbates on metal surfaces efficiently and show that bonding interpretation requires consistent choice of the density functional.