Our Research...

        Inorganic and Organometallic Chemistry and Catalysis: ligand design, novel                                    complexes,homogeneous catalysis and MOF-materials!

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Our research deals with the chemistry of transition metals bonded to novel ligands designed in our lab.

Members of the group learn a variety of technical skills including experimental synthetic tools for organic and inorganic syntheses including the manipulation of Schlenk lines and glove boxes. We all learn to make use of analytical techniques which guide our research, that includes UV-Vis, IR and multinuclear NMR spectroscopy (we not only look at 1H, 31P and 13C NMR but also exotic nuclei such as 29Si, 119Sn, 27Al, 103Rh, etc.) and two dimensional NMR experiments. Not only that, but single crystal X-Ray diffraction and other X-Ray techniques (XPS, XAS: XANES, XAFS) make us understand our compounds and materials. Finally, we get to closely interact with our theoretical colleagues as computational tools are key to the understanding of our systems.

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Our interest is in developing new highly reactive organometallics to solve some of the challenges of our society, specifically for the improvement of industrially relevant catalytic processes.

Homogenenous and MOF-supported catalytic materials are amongst the applications of our novel complexes.

Industrial development has greatly shifted towards the use of catalysts to the point that the majority of commercial chemical products involve catalytic processes at some stage of their production making them a multi-billion dollar business. By definition, catalytic reactions are recognized as environmentally friendly due to the reduced amount of reagents used and waste generated. However, owing to their physical/chemical complexity and the difficulties that in general haunt the study of reaction mechanisms, many catalytic cycles remain unsolved and their industrial implementation is mainly driven by empirical observations. One successful approach to elucidating catalytic mechanisms and thus to improve their efficiency is to employ transition metal molecular complexes in homogeneous phase as models.

 

Dual functionality phosphine ligands for transition metal complexation

Amongst the novel ligands we study, those incorporating both a group 14 element as well as a basic phosphorus atom in their structure have shown remarkable properties. Group 14 derivatives are exceptionally good sigma donors and exert a considerably high trans influence/effect, thus upon coordination they usually generate electron rich metal centers, which are in turn capable of activating otherwise inert substrates. In addition, the incorporation of phosphorous (and silicon or tin) in a ligand framework also allows for the employment of NMR spectroscopic tools. In the last years, the efforts of our research group have centered mainly on the design of pincer-like and tetrapodal phosphorous ligands functionalized with Si, Ge and Sn coordinated to second and third-row metals. We are currently extending our methodology to involve the coordination of cheaper, more environmentally-friendly first-row metals. We have succeeded in making excellent homogeneous catalysts based on Co and Ni! We have also accessed new promising Cu(I) compounds with unusual structures!

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Homogeneous catalysis

In particularly, our group wants to target catalytic dehydrogenative silylation (DHSi) and borylation (DHB) of alkenes to selectively synthesize unsaturated functionalized molecules (alkenyl-silanes and boranes) for a variety of applications. Other research groups around the world have targeted their synthesis making significant breakthroughs yet there remain large knowledge voids and central interrogations which must be addressed and fulfilled in order to improve selectivity, yield, reaction conditions, sustainability and substrate scope. Our research objective is to synthesize new catalysts of groups 8-10 transition metals (TM, and Mn) incorporating novel dual functionality Si, Sn- or Ge- phosphine ligands.

The targeted unsaturated products, including for example vinylorganoboronic esters, are key building blocks and possess a wide variety of applications in industry and academia from material to life sciences. Amongst others, these applications are in the synthesis of important pharmaceuticals, polymers, cross-linking agents, plastics and fine chemicals.

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Heterogeneous catalysts

A popular approach for the application of molecular catalysts in the synthetic industry is to immobilize them on mesoporous supports to overcome diffusion limitations. However, many examples of immobilized catalysts onto solid supports have shown excellent design and even activity and selectivity as catalytic models, yet only a few are industrially relevant because the study of their lifetimes is often neglected. Recent developments in the field of surface organometallic catalysis suggest that the key to developing successful industrial catalytic materials lies on designing efficient and principally, highly robust materials. We want to investigate how the use of heterogeneous catalysts can enhance or modify the selectivity of the current homogeneous catalytic systems. Out of the many support materials for molecular catalysts including zeolites, metal oxides, polymers, etc. are relevant, we have chosen to use Metal Organic Frameworks, MOFs because of their pore size and their chemical and structural stability, which can be used to design active sites at the molecular level and influence selectivity and activity.