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End date: 2024 × Start date: 2020 × End date: 2024 × Start date: 2020 × Publisher: Weinheim : Wiley-VCH × Subject: Phosphorus × WGL Institute: LIKAT ×

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Now showing 1 - 3 of 3
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    On the Reactivity of Phosphaalumenes towards C−C Multiple Bonds
    (Weinheim : Wiley-VCH, 2023) Nees, Samuel; Wellnitz, Tim; Dankert, Fabian; Härterich, Marcel; Dotzauer, Simon; Feldt, Milica; Braunschweig, Holger; Hering‐Junghans, Christian
    Heterocycles containing group 13 and 15 elements such as borazines are an integral part of organic, biomedical and materials chemistry. Surprisingly, heterocycles containing P and Al are rare. We have now utilized phosphaalumenes in reactions with alkynes, alkenes and conjugated double bond systems. With sterically demanding alkynes 1,2-phosphaalumetes were afforded, whereas the reaction with HCCH or HCCSiMe3 gave 1,4-phosphaaluminabarrelenes. Using styrene saturated 1,2-phosphaalumates were formed, which reacted further with additional styrene to give different regio-isomers of 1,4-aluminaphosphorinanes. Using ethylene, a 1,4-aluminaphosphorinane is obtained, while with 1,3-butadiene a bicyclic system containing an aluminacyclopentane and a phosphirane unit was synthesized. The experimental work is supported by theoretical studies to shed light on the mechanism governing the formation of these heterocycles.
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    On New Staudinger Type Reactions of Phosphorus Centered Biradicaloids, [P(μ-NR)]2 (R = Ter, Hyp), with Ionic and Covalent Azides
    (Weinheim : Wiley-VCH, 2020) Schulz, Axel; Hinz, Alexander; Rölke, Anne; Villinger, Alexander; Wustrack, Ronald
    Phosphorus centered biradicaloids of the type [P(μ-NTer)]2 [R = Ter = terphenyl = 2,6-bis(2,4,6-trimethylphenyl)phenyl, Hyp = tris(trimethylsilyl)silyl] were treated with covalent (R-N3) and ionic azides (AgN3 and Hg(N3)2). While the reaction with the ionic azides led exclusively to the formation of diazides, [N3P(μ-NTer)]2, triaza-diphospha-pentadienes, RN=P–N(R')–P=NR, were observed in the reaction with covalent azides featuring a Staudinger type reaction followed by PN bond rearrangement reactions. This new Staudinger type mechanism as well as the structure, bonding and thermodynamics along different reaction paths are discussed based on DFT computations.
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    Synthesis and Reactivity of Monocyclic Homoleptic Oligophosphanes
    (Weinheim : Wiley-VCH, 2021) Wellnitz, Tim; Hering‐Junghans, Christian
    This Minireview outlines the synthesis and reactivity of homoleptic, cyclic oligophosphanes, which have been known for more than 150 years. We will discuss a variety of (PR)n (n = 3,4,5,6) species and outline approaches towards their syntheses in the first part of this review. Then the unique reactivity of these inorganic ring systems will be discussed in detail with a focus on recent findings within the last 20 years. First ring expansion reactions will be described, which are mainly restricted to cyclotriphosphanes. Secondly, ring fragmentation will be highlighted, including phosphinidene transfer reactions. Furthermore, cyclooligophosphanes can be functionalized while retaining the parent ring structures. As oligophosphanes offer multiple donor sites, in a last part the coordination chemistry of these species is highlighted. We hope that this Minireview will spark further interest in this underexplored class of compounds as reagents in inorganic and organic synthesis, as well as the design of new P-containing materials.