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Author: Beweries, Torsten × Author: Spannenberg, Anke × End date: 2024 × Publisher: Weinheim : Wiley-VCH × WGL Institute: LIKAT ×

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    Dehydropolymerisation of Methylamine Borane and an N-Substituted Primary Amine Borane Using a PNP Fe Catalyst
    (Weinheim : Wiley-VCH, 2020) Anke, Felix; Boye, Susanne; Spannenberg, Anke; Lederer, Albena; Heller, Detlef; Beweries, Torsten
    Dehydropolymerisation of methylamine borane (H3B⋅NMeH2) using the well-known iron amido complex [(PNP)Fe(H)(CO)] (PNP=N(CH2CH2PiPr2)2) (1) gives poly(aminoborane)s by a chain-growth mechanism. In toluene, rapid dehydrogenation of H3B⋅NMeH2 following first-order behaviour as a limiting case of a more general underlying Michaelis–Menten kinetics is observed, forming aminoborane H2B=NMeH, which selectively couples to give high-molecular-weight poly(aminoborane)s (H2BNMeH)n and only traces of borazine (HBNMe)3 by depolymerisation after full conversion. Based on a series of comparative experiments using structurally related Fe catalysts and dimethylamine borane (H3B⋅NMe2H) polymer formation is proposed to occur by nucleophilic chain growth as reported earlier computationally and experimentally. A silyl functionalised primary borane H3B⋅N(CH2SiMe3)H2 was studied in homo- and co-dehydropolymerisation reactions to give the first examples for Si containing poly(aminoborane)s. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
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    A Comparative Study on the Thermodynamics of Halogen Bonding of Group 10 Pincer Fluoride Complexes
    (Weinheim : Wiley-VCH, 2019) Joksch, Markus; Agarwala, Hemlata; Ferro, Monica; Michalik, Dirk; Spannenberg, Anke; Beweries, Torsten
    The thermodynamics of halogen bonding of a series of isostructural Group 10 metal pincer fluoride complexes of the type [(3,5-R2-tBuPOCOPtBu)MF] (3,5-R2-tBuPOCOPtBu=κ3-C6HR2-2,6-(OPtBu2)2 with R=H, tBu, COOMe; M=Ni, Pd, Pt) and iodopentafluorobenzene was investigated. Based on NMR experiments at different temperatures, all complexes 1-tBu (R=tBu, M=Ni), 2-H (R=H, M=Pd), 2-tBu (R=tBu, M=Pd), 2-COOMe (R=COOMe, M=Pd) and 3-tBu (R=tBu, M=Pt) form strong halogen bonds with Pd complexes showing significantly stronger binding to iodopentafluorobenzene. Structural and computational analysis of a model adduct of complex 2-tBu with 1,4-diiodotetrafluorobenzene as well as of structures of iodopentafluorobenzene in toluene solution shows that formation of a type I contact occurs. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.