The Curious Case of the Allyl Ligand: A Study in Applying the 18-Electron Rule

The 18-electron rule is an incredibly powerful tool for explaining the properties and reactivities of organometallic complexes. With the rule, however, comes the difficulty of choosing a method of implementing it, i.e. what many popular texts refer to as the “donor-pair” (ionic) method or the “neutral-ligand” method. The choice becomes particularly difficult when ligands can be counted in multiple ways via the donor-pair method, as in the case of the allyl ligand. In this investigation we hope to show that a choice of counting method can be chosen based on experimental intuition, as supported by a density functional theory (DFT) investigation. The natural electronic charge of metals, the η³-π-allyl (or simply the allyl) ligand, and the η³-cyclopropenyl ligand are discussed for a variety of organometallic complexes. A variety of DFT exchange-correlation functionals and basis sets, coupled with the Natural Population Analysis method of Landis and Weinhold, reveal the allyl ligand’s charge in a complex can be traced back to its experimental precursor. These results emphasize that the 18-electron rule is not merely a bookkeeping device and that the donor-pair method in the case of the allyl ligand holds more utility than the neutral-ligand method.     

Fe loading of a carbon-supported Fe–N electrocatalyst and its effect on the oxygen reduction reaction

Carbon-supported non-noble metal catalysts with Fe as the metal and tripyridyl triazine (TPTZ) as the ligand (Fe-TPTZ/C) were synthesized using a simple chemical method. How the Fe loading in this Fe-TPTZ/C catalyst affected the ORR activity was investigated using several Fe loadings: 0.2, 0.4, 0.7, 2.7, 4.7, 5.8 and 7.8 wt%. The as-prepared catalysts were then heat-treated at 800 °C in an N₂ environment to obtain catalysts of Fe–N/C. Energy dispersive X-ray spectroscopy (EDX) was used to identify the Fe–N/C catalysts. These Fe–N/C catalysts showed significant ORR activity improvement over the as-prepared Fe-TPTZ/C catalysts. The kinetics of the ORR catalyzed by the catalysts with different Fe loadings was studied using the rotating disk electrode technique. It was observed that a 4.7 wt% Fe loading yielded the best catalytic ORR activity. Regarding the overall ORR electron transfer number, it was found that as the catalyst's Fe loading increased, the overall ORR electron transfer number changed from 2.9 to 3.9, suggesting that increasing the Fe loading could alter the ORR mechanism from a 2-electron to a 4-electron transfer dominated process. The Tafel method was also used to obtain one important kinetic parameter: the exchange current density. A fuel cell was assembled using a membrane electrode assembly with 4.7 wt% Fe loaded Fe–N/C as the cathode catalyst, and the cell was tested for both performance and durability, yielding a 1000-h lifetime.     

Study on the catalytic behavior of metal acetylacetonates for epoxy curing reactions

Metal acetylacetonates are effective latent catalysts for epoxy/anhydride systems. A screen test on the catalytic behavior of metal acetylacetonate shows that this system offers a wide range of curing latency and material properties. It can be inferred that the curing behavior is closely related to the bonding strength of the metal ion to the ligand. Isothermal kinetic study on the catalytic behavior of metal chelates with first‐row transition metal ions is conducted and analyzed by using an autocatalytic model. It is found that the activation energy of the system containing the divalent metal chelates follows the Irving and Williams rule. The activation energies of the reaction obtained in the kinetic study are compared with the dissociation energies of the metal/ligand bond and the results are discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1572–1579, 2002     

Non-metal catalytic synthesis of graphene from a polythiophene monolayer on silicon dioxide

Direct synthesis of graphene without metal catalysts on a dielectric substrate is a major goal in graphene-based electronics and is an increasingly popular nanotechnology alternative to metal oxide semiconductor technology. However, current methods for the synthesis of these graphenes have many limitations, including the use of metal catalyst. Herein, we report a facile approach to the direct synthesis of graphene sheets based on the self-assembled monolayers (SAMs) technique. The new method for metal catalyst-free direct synthesis of a graphene sheet is through a solution-processable, inexpensive, easy, and reproducible cross-linked polythiophene self-assembled monolayer (SAM) that is formed via the [4 + 2] π cycloaddition reaction of π-electron conjugated thiophene layer self-assembled on the dielectric silicon dioxide substrate. The bifunctional molecules were carefully designed to create an SAM via silanization of alkoxy silane groups on the SiO₂ substrate, and at the other end, a thin cross-linked polythiophene layer via a [4 + 2] π-electron cycloaddition reaction of π-electron conjugated thiophene SAM. By heating the cross-linked polythiophene SAM up to 1000 °C under a high vacuum, single-layered or few-layered graphene sheets were successfully prepared on the dielectric silicon oxide substrate.     

Continuous Chirality Measure in Reaction Pathways of Ruthenium‐Catalyzed Transfer Hydrogenation of Ketones

Here we report theoretical studies on the ruthenium‐catalyzed reduction of acetophenone (and 2‐hexanone) with the intent of understanding the relative roles of catalyst and substrate along the reaction path. Overall ten reaction pathways are examined. The first eight are for acetophenone: they arise from the presence of two catalysts, with the more enantioselective one labeled 1 , and the poorer one labeled 2 , multiplied by the two configurations that the metal center of the catalysts can assume, multiplied by the two approaches, Re‐ and Si‐side, of the substrate to the catalyst. Two pathways are examined for 2‐hexanone and entail the two approaches to the ketone of the more effective catalyst. Density functional theory calculations provide structures of the minima and transition states, which subsequently have been assessed with the “continuous chirality measure” model developed by Avnir and collaborators. The picture that emerges is that the asymmetric induction is due to the interplay between the organometallic system and the organic substrate. This is effective only for catalyst 1 , which can interact effectively with acetophenone along only one in four of the reaction pathways, but not for 2 for which two out of four pathways are opened. For the hydrogenation of 2‐hexanone, the same catalyst 1 cannot produce enantiomeric excesses because the conformation of the substrate in the transition state induced by the catalyst has a relative low chirality.     

Directed Evolution of Artificial Metalloenzymes

Transition metal catalysis in asymmetric transformations plays a pivotal role in modern synthetic organic chemistry, with these catalysts being tuned by systematic variation of the chiral ligand. More than three decades ago it was recognized that an alternative approach is possible, namely the anchoring of an achiral ligand/metal entity in an appropriate protein host, with formation of an artificial metalloenzyme (hybrid catalyst). However, this procedure delivers a single transition metal catalyst, with high enantioselectivity being a matter of chance. In view of this restriction, we proposed in 2001/2002 the concept of directed evolution of such hybrid catalysts. The most intensively studied system involves biotinylated phosphine/metal entities which are non-covalently anchored to streptavidin. The present review summarizes progress in this intriguing area of research. It includes the assessment of the requirements of a given Darwinian system to be successful, and offers hints on how to achieve success in future studies.     

Design strategies for the molecular level synthesis of supported catalysts

Supported catalysts, metal or oxide catalytic centers constructed on an underlying solid phase, are making an increasingly important contribution to heterogeneous catalysis. For example, in industry, supported catalysts are employed in selective oxidation, selective reduction, and polymerization reactions. Supported structures increase the thermal stability, dispersion, and surface area of the catalyst relative to the neat catalytic material. However, structural and mechanistic characterization of these catalysts presents a formidable challenge because traditional preparations typically afford complex mixtures of structures whose individual components cannot be isolated. As a result, the characterization of supported catalysts requires a combination of advanced spectroscopies for their characterization, unlike homogeneous catalysts, which have relatively uniform structures and can often be characterized using standard methods. Moreover, these advanced spectroscopic techniques only provide ensemble averages and therefore do not isolate the catalytic function of individual components within the mixture. New synthetic approaches are required to more controllably tailor supported catalyst structures. In this Account, we review advances in supported catalyst synthesis and characterization developed in our laboratories at Northwestern University. We first present an overview of traditional synthetic methods with a focus on supported vanadium oxide catalysts. We next describe approaches for the design and synthesis of supported polymerization and hydrogenation catalysts, using anchoring techniques which provide molecular catalyst structures with exceptional activity and high percentages of catalytically significant sites. We then highlight similar approaches for preparing supported metal oxide catalysts using atomic layer deposition and organometallic grafting. Throughout this Account, we describe the use of incisive spectroscopic techniques, including high-resolution solid state NMR, UV-visible diffuse reflectance (DRS), UV-Raman, and X-ray absorption spectroscopies to characterize supported catalysts. We demonstrate that it is possible to tailor and isolate defined surface species using a molecularly oriented approach. We anticipate that advances in catalyst design and synthesis will lead to a better understanding of catalyst structure and function and, thus, to advances in existing catalytic processes and the development of new technologies.     

乙烯和环烯烃共聚用有机金属催化剂

配位催化共聚是制备环烯烃共聚物的主要方法，目前商品化的环烯烃共聚物主要由乙烯与降冰片烯或者四环十二碳烯共聚得到。共聚单体及其含量是决定环烯烃共聚物性能的关键因素，而决定共聚单体含量的最核心因素是催化剂。本文从催化剂结构的角度出发，综述了乙烯和降冰片烯/四环十二碳烯共聚用有机金属催化剂，从双茂有机金属催化剂、单茂有机金属催化剂、非茂有机金属催化剂、后过渡金属催化剂等部分进行论述，同时论述了催化剂结构及关键聚合工艺（如温度、压力、单体浓度等）对催化活性及共聚单体插入量的重要影响。此外，由于乙烯与四环十二碳烯共聚活性低，未来针对该共聚反应的研究会继续进行。合成更多新结构的配体、开发更高活性的催化剂、构建更经济有效的反应体系将会是新的研究重点。     

二氧化碳和甲醇直接合成碳酸二甲酯研究进展

从均相及多相催化剂体系和反应条件等方面,综述了近年来二氧化碳和甲醇直接合成碳酸二甲酯的研究开发最新进展。介绍了均相催化剂体系包括有机金属烷氧基化合物、碱土金属烷氧基化合物、碱性催化剂和乙酸盐催化剂;多相催化剂体系包括负载型金属催化剂、负载型固体碱催化剂和氧化物催化剂。对催化剂及反应体系的设计、光催化剂、杂多酸催化剂、离子液体体系、助催化剂及吸水剂的使用、微波加热、膜反应器以及超临界二氧化碳溶剂体系进行了评述。     

Catalytic ethylene dimerization and oligomerization: recent developments with nickel complexes containing P,N-chelating ligands

Catalytic ethylene oligomerization represents a topic of considerable current academic and industrial interest, in particular for the production of linear alpha-olefins in the C4-C10 range, whose demand is growing fast. Identifying and fine-tuning the parameters that influence the activity and selectivity of metal catalysts constitute major challenges at the interface between ligand design, coordination/organometallic chemistry, and homogeneous catalysis. In this Account, we show how comparative studies aiming at modulating the coordinating properties of functional ligands for a metal, such as nickel, which is used in industrial processes, lead to beneficial effects in catalytic ethylene oligomerization.     

Surface organometallic chemistry on metals. Application to chemicals and fine chemicals

Some applications of surface organometallic chemistry on metals to catalysis are presented, showing the great importance of the modification of a metallic surface by organometallic compounds on its catalytic properties. The selective hydrogenation of α–β unsaturated aldehydes such as citral (Z and E) can be achieved on rhodium–tin catalysts. While rhodium alone is relatively unselective, geraniol (and nerol) can be obtained selectively (> 98%) without a significant loss of activity by use of a rhodium–tin catalyst showing a typical ligand effect of the organotin fragment on the surface. Similarly, in the isomerization of (+) 3-carene into (+) 2-carene or the dehydrogenation of butan–2–ol into methyl ethyl ketone, the selectivity into the desired product is increased by introduction of small amounts of tin which will form adatoms poisoning unselective sites. An alloying effect of tin is also presented in the dehydrogenation reaction of isobutane in isobutene. This revised version was published online in June 2006 with corrections to the Cover Date.     

Visible light‐absorbing biocompatible polymers based on L‐lactide and aminosugars: preparation and characterization

Two series of polymers with low‐molecular‐weight L ‐lactide side‐arms were prepared by ring‐opening polymerization using D ‐glucosamine and N‐acetyl‐D ‐glucosamine as polymer core molecules, and methanesulfonic acid as solvent and catalyst. This simple synthetic route does not rely on the use of organometallic catalysts, and has also proven useful to the authors for chitosan grafting with lactones. NMR spectroscopy reveals a high degree of substitution (>3), and Fourier transform infrared/NMR spectra suggest the existence of three different lactate tautomers likely to be responsible for coloration. These D ‐glucosamine‐based polymers also display glass transition temperatures approximately 10 °C above that of the human body, which points to the potential of these lactone‐grafted aminosugars with tunable amphiphilic character in the design of submicrometer‐sized drug delivery vehicles. They are also viewed as interesting hydrophobic chelating agents for catalytic transition metal centers. Copyright © 2010 Society of Chemical Industry     

Liquid phase oxidation at metal ions and complexes in constrained environments

Various approaches towards the rational design of novel catalysts based on the concept of confinement (site-isolation) of redox active metal centres in molecular sieves are reviewed. These comprise (a) substitution of T elements (Si, Al and P) in the framework of silicates, zeolites, AlPOs and SAPOs, (b) encapsulation of metal complexes in intrazeolite space (ship-in-a-bottle catalysts) and (c) grafting or tethering of metal complexes to the internal surface of the molecular sieves. Related materials - redox pillared clays, clay intercalated metal complexes, redox aerogels and metal complexes incorporated in aerogels - are also reviewed. The advantages and limitations of the various materials with regard to activity and selectivity as catalysts for liquid phase oxidations with O₂, H₂O₂ and RO₂H and stability towards leaching, are discussed.     

Investigation of ring-opening polymerization of 5-[2-{2-(2-methoxyethoxy)ethoxy}-ethoxymethyl]-5-methyl-1,3-dioxa-2-one by organometallic catalysts

To develop new polymer-based materials, the design of aliphatic carbonate has received attention and become a well-known cyclic monomer. In view of carbonate ring polymer scope, poly(trimethylene carbonate) (PTMC) has been continuously developed for further applications due to its unique degradability. PTMC bearing oligo ethylene glycol units, PTMCM-MOE3OM, were typically prepared via ring-opening polymerization (ROP) using amidine-based catalysts such as 1,8-diazabicyclo[5.4.0] undec-7-ene (DBU) and benzyl alcohol (BnOH) as an initiator. To improve the polymer molecular weight or other properties, several know-how synthetic catalysts based on organometallic complexes are under consideration as potential catalysts. With the existence of diverse classes of metallic complexes, the inorganic complexes were investigated for their catalytic activity based on tris(dimethylsilyl)amido chelating, bis(phenolate) chelating, and macrocyclic tetradentate (NNNN)-type cyclen chelating with a metal-core of tin (II), scandium (III), lutetium (III), and zinc (II). In this study, we found that involving a Zn(II) dimethylcyclen/alkoxide ligand and Mg complexes could accelerate the reaction and finish the polymerization under ambient conditions within 2 hr. Molecular weight reached 11,000 g/mol (40%) and 8,100 g/mol (> 96%). Subsequently, we concluded that Zn and Mg complexes were high reactivity for initiating the ROP of TMCM-MOE3OM upon steadily degree of polymerization.     

Precision control of radical polymerization via transition metal catalysis: from dormant species to designed catalysts for precision functional polymers

In the past decade, living radical polymerization has provided one of the most versatile methods to precisely construct designed polymer architectures with complexity and polar functionality. This process takes advantage of carbon-radical intermediates, which tolerate a variety of functional groups in monomers and reaction media. "Transition metal-catalyzed living radical polymerization", one of these living systems, has widely been employed for precision polymer synthesis. Not only can this process produce well-defined functional polymers, but it can also generate hybrids or conjugates with other (often biological) materials. Metal-catalyzed systems retain the advantages of conventional radical polymerization but distinguish themselves through a catalytic reversible halogen exchange equilibrium: the growing radical exists alongside a dormant speciesa covalent precursor capped with a terminal halogen from an initiator. The catalyst dictates the selectivity, exchange rate, and control over the polymerization. This Account provides an updated overview of our group's efforts in transition metal-catalyzed living radical polymerization with specific emphasis on the design of metal catalysts and the resulting precision polymer syntheses. With increasing use of the living processes as convenient tools for materials synthesis, researchers are currently seeking more active and versatile metal catalysts that are tolerant to functional groups. Such catalysts would enable a wider range of applications and target products, would have low metal content, could be readily removed from products, and would allow recycling. Since we first developed the "transition metal-catalyzed living radical polymerization" with RuCl 2(PPh 3) 3, FeCl 2(PPh 3) 2, and NiBr 2(PPh 3) 2, we have strived to systematically design metal catalysts to meet these new demands. For example, we have enhanced catalytic activity and control through several modifications: electron-donating or resonance-enhancing groups, moderate bulkiness, heterochelation via a ligand, and halogen-donor additives. For some catalysts, the use of amphiphilic and polymeric ligands allow efficient recovery of catalysts and convenient use in aqueous media. We have also used ligand design (phosphines) and other methods to improve the thermal stability of iron- and nickel-based catalysts and their tolerance to functional groups.     

DRIFT study of CO chemisorption on organometallics-derived Pd/MgO catalysts: the effect of chlorine

Magnesia-supported palladium catalysts were prepared from chemical vapour deposition (CVD) of [Pd(C₃H₅)(C₅H₅)] and incipient wetness impregnation of [Pd(C₃H₅)Cl]₂ and [Pd(acac)₂]. DRIFT spectroscopy of adsorbed CO on prereduced catalysts indicates that the electronic state of metal particles depends on the preparation methodology and markedly on the organometallic precursor. Inn-heptane reforming at 500°C, the highest activity and selectivity were shown by the CVD-based system. Chloride ions deriving from the impregnation solvent exchange with surface hydroxyls. Acidic Mg-Cl sites are thus formed, which induce a beneficial effect on the catalytic properties. The reforming activity collapsed when a chlorine-containing precursor was used, due to a partial coverage of the palladium surface with chemisorbed chlorine atoms.     

Influence of the nature of the platinum precursor on the surface properties and catalytic activity of alumina-supported catalysts

The influence of the nature of the metal precursor — platinum acetylacetonates and chloroplatinic acid — on the surface properties and catalytic activity of Pt/Al₂O₃ catalysts is reported. The obtained results indicate that the catalysts prepared by the organometallic route present higher metal dispersion and lower acidity compared with those prepared from H₂PtCl₆. On the other hand, XPS results showed that the state of platinum is essentially Pt⁰ in the catalysts obtained from Pt(acac)₂ while in the solids prepared by impregnation of H₂PtCl₆ there exists an important contribution of Pt⁺ species which plays a positive role in the hydrogenation of toluene. An additional hydrogen spillover due to the presence of more acidic support is also suggested as an explanation of the observed catalytic results.     

铑催化剂催化烯烃不对称加氢反应研究进展

不对称催化氢化反应具有完美的原子经济性和清洁高效等特点,是最受青睐的不对称合成方法之一。C=C、C=O、C=N的不对称加氢反应仍主要依赖过渡金属催化剂。过渡金属催化剂,尤其是铑催化剂,催化碳碳双键的不对称加氢反应仍是一个不断发展的领域。本文对近年来利用铑催化剂催化烯烃进行不对称氢化反应的研究进展进行了综述,着重介绍了铑-双膦配体催化体系催化烯烃不对称加氢反应的催化机理,以及铑催化剂在烯胺、不饱和羧酸及衍生物、烯醇酯和非官能团烯烃不对称氢化中的应用,并通过对现有文献的总结指出了今后铑催化剂催化烯烃氢化反应的研究重点,即:①铑-单膦配体催化烯烃不对称氢化反应的作用机理须待提出;②非官能化底物不对称催化氢化反应的手性配体亟待拓宽。     

Phase-transfer catalytic activity of polymer-supported macrocyclic polyethers

Polymer-supported crown-ethers 9 and 11 (4.5-62% ring substitution) have been obtained by the reaction of 1% crosslinked chloromethylated polystyrenes with (hydroxymethyl) and (ω-hydroxynonyl)-18-crown-6, respectively. (Hydroxymethyl) and (ω-hydroxynonyl) [2.2.2] cryptands have also been prepared and linked in a similar way to afford catalysts 10 and 12 (3-6% ring substitution). Condensation of (aminomethyl) and (ω-aminodecyl [2.2.2] crypands with carboxylated 1% crosslinked polystyrene gave catalysts 13 and 14 (5-20% ring substitution). Phase-transfer catalytic activity of polymer-supported crown-ethers and cryptands has been tested in anion promoted nucleophilic aliphatic substitutions, and compared with that of polymer-supported phosphonium salts. The results indicate that catalytic activity of crown-ethers strongly depends on the combination of three parameters: the nature of the nucleophile, the percent ring substitution, and the presence of a spacer chain. Catalytic activity of cryptands is higher than that of crown-ethers and quaternary salts with similar percent ring substitution. It is much less dependent on the nature of the anions and on the presence of a spacer chain. As for the related quaternary salts, phase-transfer reactions promoted by polymer-supported crown-ethers and cryptands follow a mechanism identical with that observed for soluble catalysts: the reactions occur in the organic shell surrounding a complexed ligand; anions are exchanged at the water-organic solvent interface, the exchange not requiring the concomitant transfer of cationic counterparts.     

Hydrothermal gasification of glucose using Raney nickel and homogeneous organometallic catalysts

Catalytic gasification of biomass to fuel gaseous in sub and super critical water is a promising method for production of sustainable energy. In this paper, a microreactor has been utilized to study the hydrothermal gasification of glucose in the presence of transition metal chelates consisting of nickel(II) acetylacetonate (Ni(acac)₂), cobalt(II) acetylacetonate (Co(acac)₂), iron(III) acetylacetonate (Fe(acac)₃) and Raney-nickel particles. The reaction temperature and pressure were 310–350 °C and 100–210 bar, respectively. Effects of addition of catalysts, reaction temperature, reaction time, glucose concentration and liquid water volume fraction on the amount of the generated gas as well as its composition were investigated. Results indicated that the presence of the organometallic compounds can slightly facilitate the rate of decomposition of glucose. This enhancement in reaction rate was more pronounced at higher concentrations of the feed (~ 0.65 M) compared with lower concentrations (~ 0.06 M). In contrast to these homogeneous catalysts, Raney-nickel catalyst improved the gas yield by a factor of 3 to 5. It has been observed that the amount of the produced gas almost doubles when the batch time increased from 3 to 30 min, while no significant change was observed from 30 to 60 min. Finally, remarks on optimization of the amount of added water into the reaction vessel are provided.