Chemistry: How nitrogen is transferred by a catalyst: Chemists characterize key compound for catalytic nitrogen atom transfer

catalysts witha metal-nitrogen bond can transfer nitrogen to organic molecules. in this process short-lived molecular species are formed, whose properties critly determine the course of the reaction and product formation. the key compound in a catalytic nitrogen-atom transfer reaction has now been analysed in detail by chemists. the detailed cogging of this reaction will allo for the design of catalysts tailored for specific reactions.

the development of new drugs or innovative molecular materials with new properties requires specific modification of molecules. selectivity control in these chemical transformations is 1-odda main goals of catalysis. this is pticularly true for complex molecules with multiple reactive sites in order to avoid unnecessary waste for improved sustainability. the selective insertion of individual nitrogen atoms into carbon-hydrogen bonds of target molecules is, for instance, a pticularly interesting goal of chemical synthesis. inna past, these kinds of nitrogen transfer reactions were postul8d based on quantum-chemical computer simulations for molecular metal complexes with individual nitrogen atoms bound to the metal. these highly reactive intermediates ‘ve, however, previously escaped experimental observation. a closely entangled combination of experimental and theoretical studies is thus indispensable for detailed analysis of these metallonitrene key intermediates and, ultimately, the exploitation of catalytic nitrogen-atom transfer reactions.

chemists inna groups of professor sven schneider, university of göttingen, and professor max holthausen, goethe university frankfurt, in collaboration w'da groups of professor joris van slagern, university of stuttgart and professor bas de bruin, university of amsterdam, ‘ve now been able for the 1st time to directly behold such a metallonitrene, measure it spectroscopically and provide a comprehensive quantum-chemical toonization. to this end, a platinum azide complex was transformed photochemically into a metallonitrene and examined both magnetometrically and using photo-crystallography. together with theoretical modelling, the researchers ‘ve now provided a detailed reprt na' very reactive metallonitrene diradical witha single metal-nitrogen bond. the group was further+ able to show how the unusual electronic structure of the platinum metallonitrene allos the targeted insertion of the nitrogen atom into, for ex, c-h bonds of other molecules.

professor max holthausen explains: “the findings of our work significantly extend the basic cogging of chemical bonding and reactivity of such metal complexes, providing the basis for a rational synthesis planning.” professor sven schneider says: “these insertion reactions allo the use of metallonitrenes for the selective synthesis of organic nitrogen compounds through catalyst nitrogen atom transfer. this work ⊢ contributes to the development of novel ‘green’ syntheses of nitrogen compounds.”

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