Thomas Zell

Hydrogenation and dehydrogenation iron pincer catalysts capable of metal-ligand cooperation by aromatization/dearomatization.

The substitution of expensive and potentially toxic noble-metal catalysts by cheap, abundant, environmentally benign, and less toxic metals is highly desirable and in line with green chemistry guidelines. We have recently discovered a new type of metal-ligand cooperation, which is based on the reversible dearomatization/aromatization of different heteroaromatic ligand cores caused by deprotonation/protonation of the ligand. More specifically, we have studied complexes of various transition metals (Ru, Fe, Co, Rh, Ir, Ni, Pd, Pt, and Re) bearing pyridine- and bipyridine-based PNP and PNN pincer ligands, which have slightly acidic methylene protons. In addition, we have discovered long-range metal-ligand cooperation in acridine-based pincer ligands, where the cooperation takes place at the electrophilic C-9 position of the acridine moiety leading to dearomatization of its middle ring. This type of metal-ligand cooperation was used for the activation of chemical bonds, including H-H, C-H (sp(2) and sp(3)), O-H, N-H, and B-H bonds. This unusual reactivity likely takes place in various catalytic hydrogenation, dehydrogenation, and related reactions. In this Account, we summarize our studies on novel bifunctional iron PNP and PNN pincer complexes, which were designed on the basis of their ruthenium congeners. Iron PNP pincer complexes serve as efficient (pre)catalysts for hydrogenation and dehydrogenation reactions under remarkably mild conditions. Their catalytic applications include atom-efficient and industrially important hydrogenation reactions of ketones, aldehydes, and esters to the corresponding alcohols. Moreover, they catalyze the hydrogenation of carbon dioxide to sodium formate in the presence of sodium hydroxide, the selective decomposition of formic acid to carbon dioxide and hydrogen, and the E-selective semihydrogenation of alkynes to give E-alkenes. These catalysts feature, compared to other iron-based catalysts, very high catalytic activities which in some cases can even exceed those of state-of-the-art noble-metal catalysts. For the iron PNP systems, we describe the synthesis of the pyridine- and acridine-based PNP iron complexes and their performances and limitations in catalytic reactions, and we present studies on their reactivity with relevance to their catalytic mechanisms. In the case of the bipyridine-based PNN system, we summarize the synthesis of new complexes and describe studies on the noninnocence of the methylene position, which can be reversibly deprotonated, as well as on the noninnocence of the bipyridine unit. Overall, this Account underlines that the combination of cheap and abundant iron with ligands that are capable of metal-ligand cooperation can result in the development of novel, versatile, and efficient catalysts for atom-efficient catalytic reactions.

Efficient Hydrogen Liberation from Formic Acid Catalyzed by a Well-Defined Iron Pincer Complex under Mild Conditions

Hydrogen liberation: An attractive approach to reversible hydrogen storage applications is based on the decomposition of formic acid. The efficient and selective hydrogen liberation from formic acid is catalyzed by an iron pincer complex in the presence of trialkylamine. Turnover frequencies up to 836 h⁻¹ and turnover numbers up to 100,000 were achieved at 40 °C. A mechanism including well-defined intermediates is suggested on the basis of experimental and computational data.

Unprecedented iron-catalyzed ester hydrogenation. Mild, selective, and efficient hydrogenation of trifluoroacetic esters to alcohols catalyzed by an iron pincer complex

The synthetically important, environmentally benign hydrogenation of esters to alcohols has been accomplished in recent years only with precious-metal-based catalysts. Here we present the first iron-catalyzed hydrogenation of esters to the corresponding alcohols, proceeding selectively and efficiently in the presence of an iron pincer catalyst under remarkably mild conditions.

Highly efficient, general hydrogenation of aldehydes catalyzed by PNP iron pincer complexes

A general protocol for the synthetically and industrially important hydrogenation of aldehydes to alcohols is reported. The reactions are catalyzed by well-defined iron pincer complexes that are capable of hydrogenation of aliphatic and aromatic aldehydes selectively and efficiently under mild conditions, with unprecedented turnover numbers.

From Ruthenium to Iron and Manganese-A Mechanistic View on Challenges and Design Principles of Base-Metal Hydrogenation Catalysts

The development of new homogenous base‐metal catalysts for hydrogenation reactions is a rapidly expanding and evolving field of research, which has the potential to provide inexpensive and sustainable alternatives for atom economic reactions and possibly contribute additional tools for hydrogen storage applications. While tremendous accomplishments in terms of catalytic activity and substrate scope have been reported over the last years, the available mechanistic information on these reactions is often very limited. The current Concept article intends to summarize, categorize and analyze mechanistic information on iron‐based hydrogenation catalysts. In addition, we present the challenges that must be tackled in the future to develop more effective and mature catalyst systems. The primary focus of this work lies on iron‐based catalysts. However, manganese‐based hydrogenation catalysts have recently attracted significant interest and a remarkable progress in their development has been made. Available mechanistic information on manganese catalysts is compared to that on iron catalysts and basic similarities and differences are discussed.

Introduction: hydrogen storage as solution for a changing energy landscape

Abstract The expansion of sustainable technologies and infrastructures for the production and delivery of energy to the final consumer and the development of new technologies for energy production, storage and distribution, are challenging and inevitable tasks. Power plants based on the combustion of fossil fuel resources or nuclear power plants are not suitable to provide energy in the future due to significant disadvantages and dangers associated with these outdated technologies. The development of new sustainable technologies for the production of energy is desirable. Besides focusing on the production step, the change in global energy landscape requires also new and improved energy storage systems. Requirements for these storage solutions will strongly depend on the application. Storing energy by producing and consuming hydrogen is in this context a very attractive approach. It may be suitable for storage of energy for transportation and also for the bulk energy storage. Due to physical restrictions of high pressure hydrogen storage, alternative techniques are developed. This is, in turn, an ongoing task with multidisciplinary aspects, which combines chemistry, physics, material science and engineering. Herein, we review the production and consumption of energy, different energy storage applications, and we introduce the concept of hydrogen storage based on hydrogenation and dehydrogenation reactions of small molecules.

CO2-based hydrogen storage – formic acid dehydrogenation

Abstract Changing demands on the energy landscape are causing the need for sustainable approaches. The shift toward alternative, renewable energy sources is closely associated with new demands for energy storage and transportation. Besides storage of electrical energy, also storage of energy by generating and consuming hydrogen (H2) is possible and highly attractive. Notably, both secondary energy vectors, electric energy and hydrogen, have practical advantages so that one should not ask “which one is better?” but “which one fits better the specific application?” Molecular hydrogen can be stored reversibly in form of formic acid (FA, HCOOH). In the presence of suitable catalysts, FA can be selectively decomposed to hydrogen and carbon dioxide (CO2). A CO2-neutral hydrogen storage cycle can be achieved when carbon dioxide serves as starting material for the production of the FA. Examples of CO2 hydrogenation to FA are known in the literature. Herein, the formal reverse reaction, the decomposition of FA to H2 and CO2 by different catalyst systems is reviewed and selected examples for reversible storage applications based on FA as hydrogen storage compound are discussed.