Browsing by Author "Hettich, Thomas D."

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    Silyl‐ and germyl‐substituted diorganophosphonites
    (2023) Hettich, Thomas D.; Rudolf, Richard; Birchall, Nicholas; Nieger, Martin; Gudat, Dietrich
    Reactions of metalated diorganophosphonite boranes with triorganosilyl and ‐germyl halides provided borane adducts of diorgano(tetryl)phosphonites. Further treatment with excess Et3N or DABCO yielded the borane‐free species (RO)2P‐ER′>3 (E=Si, Ge; R, R′=alkyl, aryl). The products of all reactions were characterized by elemental analyses and NMR data, and in selected cases by MS and single‐crystal XRD studies. Reactions of selected ligands with Ni(CO)4 and selenium were shown to produce Ni(CO)‐complexes or diorgano(tetryl) phosphonoselenoates (RO)(R′3E)P=Se, respectively, which were identified spectroscopically but could not be isolated. Evaluation of the TEP and 1JPSe coupling constants were used for a first assessment of the electron donor properties of the new molecules.
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    Synthese und Charakterisierung P-nukleophiler Diorganophosphonite und ihrer Boran-Addukte
    (2023) Hettich, Thomas D.; Gudat, Dietrich (Prof. Dr.)
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    Synthesis and ambiphilic reactivity of metalated diorgano‐phosphonite boranes
    (2021) Hettich, Thomas D.; Rudolf, Richard; Feil, Christoph M.; Birchall, Nicholas; Nieger, Martin; Gudat, Dietrich
    Unprecedented metalated phosphonite boranes were prepared from PH‐substituted precursors and silyl amides. Although potassium derivatives were thermally stable and could even be isolated and structurally characterised, lithiated analogues proved to be unstable towards self‐condensation under cleavage of LiOR at ambient temperature. Reaction studies revealed that the metalated phosphonite boranes exhibit ambiphilic character. Their synthetic potential as nucleophilic building blocks was demonstrated in the synthesis of the first stannylated phosphonite representing a new structural motif in phosphine chemistry.