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Author: Bresien, Jonas × Publisher: Weinheim : Wiley-VCH ×

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    Azadiphosphaindane-1,3-diyls: A Class of Resonance-Stabilized Biradicals
    (Weinheim : Wiley-VCH, 2021) Bresien, Jonas; Michalik, Dirk; Schulz, Axel; Villinger, Alexander; Zander, Edgar
    Conversion of 1,2-bis(dichlorophosphino)benzene with sterically demanding primary amines led to the formation of 1,3-dichloro-2-aza-1,3-diphosphaindanes of the type C6H4(μ-PCl)2N-R. Reduction yielded the corresponding 2-aza-1,3-diphosphaindane-1,3-diyls (1), which can be described as phosphorus-centered singlet biradical(oid)s. Their stability depends on the size of the substituent R: While derivatives with R=Dmp (2,6-dimethylphenyl) or Ter (2,6-dimesitylphenyl) underwent oligomerization, the derivative with very bulky R=tBuBhp (2,6-bis(benzhydryl)-4-tert-butylphenyl) was stable with respect to oligomerization in its monomeric form. Oligomerization involved activation of the fused benzene ring by a second equivalent of the monomeric biradical and can be regarded as formal [2+2] (poly)addition reaction. Calculations indicate that the biradical character in 1 is comparable with literature-known P-centered biradicals. Ring-current calculations show aromaticity within the entire ring system of 1. © 2020 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH
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    A Systematic Survey of the Reactivity of Chlorinated N2P2, NP3 and P4 Ring Systems
    (Weinheim : Wiley-VCH, 2019) Bresien, Jonas; Eickhoff, Liesa; Schulz, Axel; Suhrbier, Tim; Villinger, Alexander
    The reactivity of the four-membered NP3 ring system [RN(μ-PCl)2PR] (R=Mes*=2,4,6-tri-tert-butylphenyl) towards Lewis acids, Lewis bases, and reducing agents was investigated. Comparisons with the literature-known, analogous cyclic compounds [ClP(μ-NR)]2 (R=Ter=2,6-dimesitylphenyl) and [ClP(μ-PR)]2 (R=Mes*) are drawn, to obtain a better systematic understanding of the reactivity of cyclic NP species. Apart from experimental results, DFT computations are discussed to further the insight into bonding and electronic structure of these compounds. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
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    Trimethylsilyl Pseudohalide Adducts of GaCl3 and B(C6F5)3
    (Weinheim : Wiley-VCH, 2021) Bläsing, Kevin; Bresien, Jonas; Maurer, Steffen; Schulz, Axel; Villinger, Alexander
    Me3Si−X (X=CN, N3, OCN, and SCN) was treated with the Lewis acids GaCl3 and B(C6F5)3 in toluene yielding the desired adducts Me3Si−X→GaCl3 and Me3Si−X→B(C6F5)3. All synthesized adducts were isolated and completely characterized including single crystal structure elucidations. The different structures, thermodynamics of formation and charge transfer effects are discussed on the basis of experimental and theoretical data.