Browsing by Author "Stöckl, Yannick"

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    Diverse reactivity of a cationic N-heterocyclic phosphenium complex towards anionic substrates : substitution vs. reduction
    (2024) Feil, Christoph M.; Goerigk, Florian; Stöckl, Yannick; Nieger, Martin; Gudat, Dietrich
    A cationic N-heterocyclic phosphenium (NHP) iron tetracarbonyl complex was synthesised from the free cation and its behaviour towards various anionic reactants studied. Reactions with fluoride, chloride, and hydride sources proceeded under attachment of the anion at phosphorus to yield Fe(CO)4-complexes of neutral diazaphospholenes, while bromide and iodide reacted under addition of the anion at the metal and decarbonylation to yield NHP iron halides. Reactions with amides and organometallics were unselective. At room temperature, predominantly reduction of the cationic complex to yield a spectroscopically detectable Fe-centred radical and its deactivation products was observable. At -78 °C, CH-metalation at the heterocycle was preferred, as evidenced by the structural characterisation of a neutral borane-adduct of the metalation product of a modified NHP complex. The dimer of the Fe-centred radical formed also in reactions of chloro- and bromo-diazaphospholenes with Fe2(CO)9, which proceed not only by complexation of the P-donors as expected, but involve also oxidative addition steps and single electron transfer processes in which excess iron complex acts as the reductant. The title complex and the products isolated in the reaction studies were characterised by spectroscopic data and in many cases by XRD studies. Computational studies were employed to analyse the differing reactivity of the cationic NHP complex towards light and heavy halide ions, and to help in the assignment of the radical intermediate observed. The more diverse reactivity of the cationic NHP complexes compared to their neutral analogues is attributed to their higher electrophilicity.
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    Enantioenriched boron C,N‐chelates via chirality transfer
    (2023) Stöckl, Yannick; Tait, Ethan J.; Frey, Wolfgang; Wegner, Sascha; Claasen, Birgit; Zens, Anna; Laschat, Sabine
    Molecules stereogenic only at tetrahedral boron atoms show great promise for applications, for example as chiroptical materials, but are scarcely investigated due to their synthetic challenge. Hence, this study reports a two-step synthesis of enantioenriched boron C,N-chelates. First, the diastereoselective complexation of alkyl/aryl borinates with chiral aminoalcohols furnished boron stereogenic heterocycles in up to 86 % yield and d.r. >98 : 2. Treatment of these O,N-complexes with chelate nucleophiles was surmised to transfer the stereoinformation via the ate-complex into the C,N-products. This chirality transfer succeeded by substitution of the O,N-chelates with lithiated phenyl pyridine to give boron stereogenic C,N-chelates in up to 84 % yield and e.r. up to 97 : 3. The chiral aminoalcohol ligands could be recovered after isolation of the C,N-chelates. The chirality transfer tolerated alkyl, alkynyl and (hetero-)aryl moieties at boron and could be further extended by post-modification: transformations such as catalytic hydrogenations or sequential deprotonation/electrophilic trapping were feasible while maintaining the stereochemical integrity of the C,N-chelates. Structural aspects of the boron chelates were studied by variable temperature NMR and X-ray diffraction.