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.     

Biometallorganische Chemie: Ein faszinierendes Forschungsgebiet

Bioorganometallic Chemistry is a new research area in which organometallic compounds are coupled with biomolecules (sugars, peptides, DNA and its constituents, steroides, vitamines, enzymes). In a narrow sense such organometallic complexes occur in nature (vitamin B₁₂), have a biological function (e.g. nickel enzymes in bacterias) or are of potential medical use (as novel drug or as marker for biomolecules). In a wider sense bioorganometallic chemistry includes simply metal complexes which besides organometallic ligands (e.g. CO, π‐hydrocarbon) have a biomolecule as ligand (e.g. with interesting structures, for catalysis).     

Electrochemical Synthesis and Structure Analysis of Neocoenzyme B12 – An Epimer of Coenzyme B12 with a Remarkably Flexible Organometallic Group

In neocoenzyme B₁₂ (=(5′-deoxy-5′-adenosyl)-13-epicob(III)alamin; 5 ), an epimer of coenzyme B₁₂ ( 1 ), the organometallic group and a propanamide side chain of the vitamin-B₁₂ ligand compete for the same region in space. Interesting consequences for structure and organometallic reactivity of this isomer of 1 are to be expected. Neocoenzyme B₁₂ ( 5 ; 89% yield) and methyl-13-epicobalamin ( 6 ; 88% yield) were prepared from neovitamin B₁₂ ( 4 ) by electrochemical means (Fig. 3). The solution structure of the organometallic neovitamin-B₁₂ derivative 5 was analyzed by homonuclear and heteronuclear NMR spectroscopy. Comparison of the structures of 1 and 5 informed on the structural consequences of the epimerization at C(13) and revealed a remarkable flexibility of the organometallic group in 5 . In 5 , both sterically interacting functionalities (organometallic group and propanamide side chain at C(13)) adapt their conformations dynamically to avoid significant mutual clashes. As one consequence of this structural adaptation, the major conformations of 5 feature counterclockwise and clockwise reorientations of the organometallic ligand with respect to its crystallographically determined position in coenzyme B₁₂ ( 1 ). One of the dominant conformers of 5 exhibits an orientation of the organometallic functionality similar to that found in the crystal structure of the coenzyme-B₁₂-dependent methylmalonyl CoA mutase. The present NMR study also revealed the significant population of syn-conformers of the organometallic adenosine group, another remarkable feature of the solution structure of 5 .     

The Computational Road to Better Catalysts

Computational studies, especially those that use density functional theory (DFT), have become pervasive in the characterization, mechanistic study, and optimization of homogeneous organometallic catalysts, and the “rational” design of such catalysts seems within reach once more. But how advanced, user‐friendly, and reliable are the computational tools that are currently available? Here we summarize the current state of the art for predictive computational organometallic chemistry in reference to the different stages of catalyst development by considering characterization, mechanistic studies, fine‐tuning/optimization, and evaluation of novel designs. We also assess critically where the strengths and weaknesses of computational studies lie and hence map out the road ahead for the design and discovery of novel catalysts in silico and in combination with targeted experimental studies.     

Nanoporous materials: a good opportunity for nanosciences

This paper emphasizes the wide possibilities open to organometallic chemistry by the bottom-up approach for nanosciences. In this new field of research, organometallic chemistry and coordination chemistry are in position to play a very important role in the development of nanomaterials. At first, organometallic and coordination chemistries will be the mothers of plenty of nanotools, which are the elemental bricks of nanosciences. The nanomaterials are obtained from them either by inclusion in a matrix (Nanocomposites) or by grafting methods (grafted nanomaterials). However, the most exciting field of investigation are the nanostructured hybrid materials which permit to open new fields of investigation such as self-organization of organic moieties or the coordination chemistry in the solid. Some examples are given. Moreover, the organometallic chemistry performed on both the framework and the pores of the nanoporous solids obtained by sol-gel chemistry in the presence of structure directing agents is opening the way to smart materials. These materials will have the ability to couple interactively two different properties.     

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.     

Synthesis, processing and properties of conjugated polymer networks

Despite the diverse research activities focused on the chemistry, materials science and physics of conjugated polymers, the feature of conjugated cross-links, which can provide electronic communication between chains, has received little attention. This situation may be a direct consequence of the challenge to introduce such links while retaining adequate processability. Focusing on recent studies of materials for which charge transport or electrical conductivity data are available, this feature article attempts to present an overview of the synthesis, processing and electronic properties of conjugated polymer networks. For the purpose of this discussion, two distinctly separate architectures-featuring covalent cross-links on the one hand and non-covalent organometallic bridges on the other-are treated in separate sections. The available data indicate that cross-linking can have significant benefits for intermolecular charge transfer if the polymers are carefully designed.     

Clean coupling of unfunctionalized porphyrins at surfaces to give highly oriented organometallic oligomers

The direct coupling of complex, functional organic molecules at a surface is one of the outstanding challenges in the road map to future molecular devices. Equally demanding is to meet this challenge without recourse to additional functionalization of the molecular building blocks and via clean surface reactions that leave no surface contamination. Here, we demonstrate the directional coupling of unfunctionalized porphyrin molecules--large aromatic multifunctional building blocks--on a single crystal copper surface, which generates highly oriented one-dimensional organometallic macromolecular nanostructures (wires) in a reaction which generates gaseous hydrogen as the only byproduct. In situ scanning tunneling microscopy and temperature programmed desorption, supported by theoretical modeling, reveal that the process is driven by C-H bond scission and the incorporation of copper atoms in between the organic components to form a very stable organocopper oligomer comprising organometallic edge-to-edge porphyrin-Cu-porphyrin connections on the surface that are unprecedented in solution chemistry. The hydrogen generated during the reaction leaves the surface and, therefore, produces no surface contamination. A remarkable feature of the wires is their stability at high temperatures (up to 670 K) and their preference for 1D growth along a prescribed crystallographic direction of the surface. The on-surface formation of directional organometallic wires that link highly functional porphyrin cores via direct C-Cu-C bonds in a single-step synthesis is a new development in surface-based molecular systems and provides a versatile approach to create functional organic nanostructures at surfaces.     

Self-supported organometallic rhodium quinonoid nanocatalysts for stereoselective polymerization of phenylacetylene

Heterogeneous self-supported organometallic nanocatalysts (ONs) were synthesized by treatment of the eta6-pi-hydroquinone rhodium complex [(1,4-hydroquinone)Rh(COD)]+ with Al(Oi-Pr)3. The organometallic nanocatalysts, the size of which can be controlled by alteration of the reaction conditions, show high catalytic activities in the stereoselective polymerization of phenylacetylene to produce cis-poly(phenylacetylene). A key feature of the ON catalyst synthesis is a facile eta6 to eta4 hapticity change occurring in the quinonoid ring, which is triggered by deprotonation of the -OH groups by Al(Oi-Pr)3, with concomitant coordination of the quinone oxygen atoms to the aluminum.     

Cobalt carbaporphyrin-catalyzed cyclopropanation

Cobalt complexes of N-confused porphyrins and benziphthalocyanine, which both feature organometallic bonds at the macrocycle cores, catalyze the cyclopropanation of styrene with a higher trans-selectivity than the corresponding porphyrin and phthalocyanine complexes.     

Hydrogen-atom abstraction from Ni(I) phosphido and amido complexes gives phosphinidene and imide ligands

Hydrogen-atom abstraction from M-E(H) to generate M═E-containing complexes (E = PR, NR) is not well studied because only a few complexes are known to undergo such reactions. Hydrogen-atom abstraction from nickel(I) phosphide and amide complexes led to the corresponding phosphinidene and imide compounds. These reactions are unparalleled in the organometallic chemistry of nickel and feature an unusual example of a transition-metal phosphinidene synthesized by hydrogen-atom abstraction.     

Photochromism of organometallic compounds with structural rearrangement

This article introduces photochromic properties together with structures of organometallic compounds that undergo photo-induced structural rearrangement. The aim of this review is to survey the research on photochromism by using organometallics which possess by their own nature the properties responsible for the photochromism such as bonding and structural fluxionality, electronic state fluctuation, and photochemically active characteristic in both solution and the solid state. Therefore, the organometallics which include the well-characterized organic photochromic moieties, considered to be derivatives of such kinds of organic photochromic compounds, are excluded in this article. Mono-, di-, and poly-nuclear organometallic compounds are presented based on the reaction types such as linkage isomerization, haptotropic rearrangement, and reorganization of metal–ligand and/or metal–metal bonds. Very recently, the crystalline-state photochromism is becoming an attractive field of photochromic chemistry. As a demonstrative example, the photochromism of organometallic rhodium dinuclear complexes having a dithionite ligand (μ-O₂SSO₂), which shows 100% reversible interconversion in the crystalline-state and have been developed in the authors’ laboratory, will be discussed.     

Novel estradiol derivatives labeled with Ru,W, and Co complexes. Influence on hormone-receptor affinity of several organometallic groups at the 17 alpha position

In order to elucidate the extent to which recognition of the estrogen receptor is influenced by addition of an organometallic substituent at the 17 alpha position, modification of 17 beta-estradiol at this position was carried out by using the organometallic groups -C identical to C(eta 5-C5H4)RuCp, CH2-(eta 5-C5H4)RuCp, -C identical to C-(eta 5-C5H4)-W(CO)3(Me), -(C identical to CCHO)Co2(CO)6, and -(C identical to CCH2OH)Co2(CO)6. The relative binding affinity (RBA) values for estradiol receptor alpha showed that recognition was good (RBA between 20 and 13.5%) when the organometallic moiety was attached at the end of a rigid alkyne spacer. However, the affinity of the modified hormone for the receptor was severely reduced (RBA = 1%) for a substituent such as -CH2-(eta 5-C5H4)RuCP, in which the spacer is reduced to a single flexible sp3 carbon atom, allowing the organometallic moiety greater freedom of movement around the attachment point. The RBA values found were in agreement with results obtained from a molecular-modeling study in which 5, an organometallic hormone with a rigid spacer, or 7, a molecule with a flexible spacer, was inserted into the cavity of the recently characterized Ligand-Binding Domain of estrogen receptor alpha.     

Alternating current polarography of metal carbonyl complexes in nonaqueous solvents

Using commercially available instrumentation, a supporting electrolyte and electrode system was devised which permits ac polarography of organometallic compounds, transition metal complexes, and other substances in nonaqueous solvents such as methanol, N,N-dimethylformamide, or acetonitrile. The first two solvents mentioned were found to be far superior to the latter. Tetrabutylammonium perchlorate electrolyte (0.1 M or less) in methanol, for example, affords a fairly flat baseline in the applied dc potential range of 0 to ?3 V with well-shaped voltammetric peaks for most reducible substances. A unique feature of the method, which permits one to easily obtain replicable polarograms and peak potentials, is the use of a mercury pool auxiliary electrode rather than the usual platinum or tungsten electrodes.     

Surface organometallic chemistry on metals: a novel and effective route to custom-designed bimetallic catalysts

The synthesis, characterization and catalytic properties of new materials obtained by reaction of organometallic complexes of groups IIb, IVa, and VIa with the surface of metallic particles are reviewed. Two types of materials may be obtained by surface organometallic chemistry on metals: metal particles covered with organometallic fragments, and bimetallic particles of predetermined composition. Characterization of the organometallic fragments on the metal particles has demonstrated their thermal stability. These particles covered with surface organometallic fragments are new catalytic materials, highly selective in several reactions such as the hydrogenation of α,β-unsaturated aldehydes, ethyl pyruvate, nitrobenzene, acrylonitrile, and olefins. The bimetallic particles without organometallic fragments are also highly active and selective for a variety of reactions such as hydrogenolysis of various alkanes and hydrogenolysis of esters. For these systems, the concept of “site isolation” has been advanced to account for the high selectivity of the reactions.     

The effect of solvent upon the rates and mechanisms or organometallic rections. : I. General aspects

The data reported to date on the effect of solvent upon the rates and mechanisms of organometallic reactions have been analysed and discussed and indicate that the effect is very complex. The analysis also shows that there is no overall explanation for the effect and that indeed such an explanation seems at present to be non-existent.It is suggested that the problem may be successfully approached through a study of the effect of the solvent upon the redistribution of organic groups between organometallic molecules. In these reactionis, not only the kinetics of the reactions in various solvents should be studied but also identification of the organometallic complexes is essential as well as the electronic structures and geometries of the complexes in the crystalline phase and in solution.     

Chiral nonracemic late-transition-metal organometallics with a metal-bonded stereogenic carbon atom: development of new tools for asymmetric organic synthesis

Transition-metal-catalyzed cross-coupling reactions and the Heck reaction have evolved into powerful tools for the construction of carbon-carbon bonds. In most cases, the reactive organometallic intermediates feature a carbon-transition-metal sigma bond between a sp(2)-hybridized carbon atom and the transition metal (Csp(2)--TM). New, and potentially more powerful approach to transition-metal-catalyzed asymmetric organic synthesis would arise if catalytic chiral nonracemic organometallic intermediates with a stereogenic sp(3)-hybridized carbon atoms directly bonded to the transition metal (C*sp(3)--TM bond) could be formed from racemic or achiral organic substrates, and subsequently participate in the formation of a new carbon-carbon bond (C*sp(3)-C) with retention of the stereochemical information. To date, only a few catalytic processes that are based on this concept, have been developed. In this account, both "classical" and recent studies on preparation and reactivity of stable chiral nonracemic organometallics with a metal-bonded stereogenic carbon, which provide the foundation for the future design of new synthetic transformations exploiting the outlined concept, are discussed, along with examples of relevant catalytic processes.     

New method for C-H arylation/alkylation at α-position of cyclic aliphatic ethers by iron-oxide mediated reaction

We report a new and efficient iron oxide catalyzed cross-coupling reaction between organometallic species such as alkyl/arylmagnesium halides or organolithium species and α-hydrogen bearing cyclic unbranched and branched aliphatic ethers via activation of C(sp(3))-H. In the presence of 1 mol% of iron oxide, five and six membered unbranched cyclic ethers such as tetrahydrofuran and tetrahydropyran gave good to excellent yields of cross-coupled products. Whereas, in case of branched ether such as 2-methyltetrahydrofuran, it was observed that the arylation occurred at both the sides and gave moderate yields of a mixture of regioisomers. Among the organometallic species used, alkyl organometallic reagents gave less yields as compared to aryl organometallics.     

A personal account of some dinitrogen and organometallic chemistry research at the University of Sussex

This article reviews the development of dinitrogen chemistry and some associated organometallic chemistry at the University of Sussex with which the author was directly involved. The establishment of the basic heavy-element halide phosphine chemistry laid the ground for the discovery of dinitrogen complexes of rhenium, osmium, molybdenum and tungsten. From there, some of the first well-defined reactions of coordinated dinitrogen (especially protonation and alkylation) were discovered and the essential mechanisms of such reactions were established. This allowed the development of models for the action of nitrogenases that are still probably the best available. Later work has produced similar models in iron chemistry and a range of organometallic chemistry has been uncovered in the effort to discover parallels between the basic organometallic chemistry of substances such as metal carbonyls, dinitrogen complexes and hydrides in their interactions with acetylenes and cyclpropene.     

Metal-Based Multihelicenic Architectures

The preparation of multihelicenic systems by conventional organic synthesis is a challenging task and under continuous development. In parallel, using complexing units grafted to or incorporated within the helicene core and taking advantage of coordination/organometallic chemistry constitutes a powerful strategy to obtain multihelicenic structures. This Minireview focuses on the state-of-the-art preparation of metal-based multihelicenic architectures such as coordination-driven supramolecular assemblies and organometallic architectures. Their properties and their applications are presented.