5 research outputs found

    A Dialkylsilylene-Pt(0) Complex with a DVTMS Ligand for the Catalytic Hydrosilylation of Functional Olefins

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    A platinum(0) complex, bearing a 1,3-divinyl-1,1,3,3-tetra­methyl­disiloxane (DVTMS) and an isolable dialkylsilylene ligand, was successfully synthesized by the reaction between the dialkylsilylene and Karstedt’s catalyst. The downfield-shifted <sup>29</sup>Si NMR resonance, the smaller <sup>1</sup><i>J</i><sub>Si,Pt</sub> value, and the longer Si–Pt distance in this complex relative to the corresponding parameters in related bis­(phosphine)-coordinated silylene-platinum complexes suggest weaker π-back-donation from the Pt center to the silylene, which is, however, still significant when compared to related DVTMS-ligated Pt complexes bearing <i>N</i>-heterocyclic carbenes, <i>N</i>-heterocyclic two-coordinate silylenes, or base-stabilized three-coordinate silylenes. The title complex displays excellent catalytic activity in the hydrosilylation of terminal olefins that contain functional groups such as epoxide and amine moieties

    Anthryl-Substituted 3‑Silylene-2-silaaziridine Obtained by Isomerization of Disilacyclopropanimine: An Exocyclic Silene Showing a Distinct Intramolecular Charge Transfer Transition

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    An anthryl-substituted exocyclic silene, 3-silylene-2-silaaziridine, was synthesized by isomerization of the corresponding disilacyclopropanimine. The UV–vis spectrum of the silene shows a distinct intramolecular charge transfer (ICT) transition from the π orbital of the SiC double bond to the π* orbital of the anthryl moiety. The relatively high-lying π­(SiC) orbital of the 3-silylene-2-silaaziridine moiety and the low-lying π* orbital of the anthryl group would be responsible for the distinct ICT band

    Anthryl-Substituted 3‑Silylene-2-silaaziridine Obtained by Isomerization of Disilacyclopropanimine: An Exocyclic Silene Showing a Distinct Intramolecular Charge Transfer Transition

    No full text
    An anthryl-substituted exocyclic silene, 3-silylene-2-silaaziridine, was synthesized by isomerization of the corresponding disilacyclopropanimine. The UV–vis spectrum of the silene shows a distinct intramolecular charge transfer (ICT) transition from the π orbital of the SiC double bond to the π* orbital of the anthryl moiety. The relatively high-lying π­(SiC) orbital of the 3-silylene-2-silaaziridine moiety and the low-lying π* orbital of the anthryl group would be responsible for the distinct ICT band

    Synthesis and Functionalization of a 1,4-Bis(trimethylsilyl)tetrasila-1,3-diene through the Selective Cleavage of Si(sp<sup>2</sup>)–Si(sp<sup>3</sup>) Bonds under Mild Reaction Conditions

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    Although the oxidative coupling of disilenides, i.e., the disilicon analogues of vinyl anions, represents a promising route to extend the conjugation between SiSi double bonds, previously reported synthetic routes to disilenides involve strongly reducing conditions. Herein, we report a novel synthetic route to disilenides from stable disilenes via the selective cleavage of Si­(sp<sup>2</sup>)–Si­(sp<sup>3</sup>) bonds under milder reaction conditions. Using this method, a 1,4-bis­(trimethylsilyl)­tetrasila-1,3-diene (<b>5</b>) was synthesized from the corresponding silyl-substituted disilene. Moreover, Et<sub>3</sub>Si-substituted tetrasila-1,3-diene <b>7</b> was synthesized via tetrasila-1,3-dien-1-ide <b>6</b>, which is the first example of a functionalized tetrasila-1,3-diene

    Hydrogen Bonds-Enabled Design of a <i>C</i><sub>1</sub>‑Symmetric Chiral Brønsted Acid Catalyst

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    We have developed new <i>C</i><sub>1</sub>-symmetric, chiral bis-phosphoric acids with an electron-withdrawing group as one of the two substituents. This <i>C</i><sub>1</sub>-symmetric, chiral bis-phosphoric acid with a pentafluorophenyl group performs exceptionally well in the asymmetric Diels–Alder reaction of acrolein, methacrolein, and α-haloacroleins with substituted amidodienes. Control over the atropisomeric catalyst structure, enhancement of the catalytic activity, and differentiation of the asymmetric reaction space is possible by the remote control of the pentafluorophenyl group. Furthermore, we have conducted theoretical studies to clarify the roles of both intra- and intermolecular hydrogen bonds in the <i>C</i><sub>1</sub>-symmetric chiral environment of chiral bis-phosphoric acid catalysts. The developed strategy, <i>C</i><sub>1</sub>-symmetric catalyst design through hydrogen bonding, is potentially applicable to the development of other chiral Brønsted acid catalysts
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