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ERC

MIXMETAPPS Report Summary

Project ID: 279590
Funded under: FP7-IDEAS-ERC
Country: United Kingdom

Final Report Summary - MIXMETAPPS (Tailoring Mixed-Metal Chemistry for Frontier Synthetic and Catalytic Applications)

One of the global challenges for synthetic chemists is to improve and expand the catalogue of reagents available, searching for new compounds that can offer enhanced reactivities but also superior selectivities and compatibility with a wide range of different substrates. Furthermore, reactions should be atom economical, safe to the environment, use greener solvents, be carried out under mild conditions, be catalytic, and ideally not involve rare, expensive or toxic metals. MixMetApps has been specifically designed to meet some of these challenges faced by synthetic and organometallic chemists, by developing new innovative mixed-metal reagents, namely cooperative bimetallics, prepared by combining two different metals with distinct polarities within the same molecule. By using this mixed-metal approach we can instil into these compounds a new cooperative set of chemical properties and reactivity profiles, which extend far beyond the confines of traditional monometallic chemistry. Appealing to inorganic, synthetic organic, organometallic, catalytic and theoretical chemists, this research therefore offers breadth and depth as well as vast untapped potential.
Firstly, using two different synthetic methodologies (interlocking co-complexation and salt
metathesis reactions), we have constructed a library of new heterobimetallic hybrids which combine metals of different oxidation state and polarity.
Exploring the application of these reagents in organic synthesis and by systematically trapping key reaction intermediates, we have uncovered new bimetallic-mediated methodologies to perform key bond-forming processes. By modifying the steric and electronic properties of the anionic ligands present in these heterobimetallic reagents, we can facilitate novel cascade activation of N-heterocyclic molecules, such as 1,3 benzo-azoles, which leads to the ring opening and functionalisation of the azole rings, ultimately enabling the isolation of the homocoupled products after hydrolysis and
oxidation steps in excellent yields without the need of transition metal catalysts.
A core aspect of the project is to screen the reactivity of these reagents in fundamental organi reactions not only stoichiometrically, but also catalytically. Building on some of the already acquired knowledge on the reactivity patterns of these bimetallic hybrid reagents in the stoichiometric studies, we have pioneered the use of these reagents in catalytic transformations.
Extending our bimetallic approach to divalent open-shell transition metals such as Fe(II) and Mn(II), has enabled the opening up of new and exciting lines of work centred on synergic catalysis and supramolecular design.
One of the key aspirations of the project was to profit on the knowledge acquired in the synthesis, reactivity and constitution of heterobimetallic reagents for the development of new approaches, which should allow crossing the hitherto unexplored frontier between organometallic and aqueous chemistry. This important target has been accomplished by pioneering the use of classical organolithium and organomagnesium reagents in Deep Eutectic Solvents (DES) which allow the chemoselective alkylation and arylation of unsaturated organic molecules while operating at room temperature, under air and in protic solvent mixtures (even including water!).

Reported by

UNIVERSITY OF STRATHCLYDE
United Kingdom
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