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Coordination Chemistry of Diiodine and Implications for the Oxidation Capacity of the Synergistic Ag+/X2 (X=Cl,Br, I) System 下载免费PDF全文
Dr. Przemysław J. Malinowski Dr. Daniel Himmel Prof. Dr. Ingo Krossing 《Angewandte Chemie (International ed. in English)》2016,55(32):9262-9266
The synergistic Ag+/X2 system (X=Cl, Br, I) is a very strong, but ill‐defined oxidant—more powerful than X2 or Ag+ alone. Intermediates for its action may include [Agm(X2)n]m+ complexes. Here, we report on an unexpectedly variable coordination chemistry of diiodine towards this direction: ( A )Ag‐I2‐Ag( A ), [Ag2(I2)4]2+( A ?)2 and [Ag2(I2)6]2+( A ?)2?(I2)x≈0.65 form by reaction of Ag( A ) ( A =Al(ORF)4; RF=C(CF3)3) with diiodine (single crystal/powder XRD, Raman spectra and quantum‐mechanical calculations). The molecular ( A )Ag‐I2‐Ag( A ) is ideally set up to act as a 2 e? oxidant with stoichiometric formation of 2 AgI and 2 A ?. Preliminary reactivity tests proved this ( A )Ag‐I2‐Ag( A ) starting material to oxidize n‐C5H12, C3H8, CH2Cl2, P4 or S8 at room temperature. A rough estimate of its electron affinity places it amongst very strong oxidizers like MF6 (M=4d metals). This suggests that ( A )Ag‐I2‐Ag( A ) will serve as an easily in bulk accessible, well‐defined, and very potent oxidant with multiple applications. 相似文献
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Aishabibi Kassymbek Sergei F. Vyboishchikov Bulat M. Gabidullin Denis Spasyuk Melanie Pilkington Georgii I. Nikonov 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(50):18270-18275
In situ oxidation of the GaI compound NacNacGa by either N2O or pyridine oxide results in the generation of a labile monomeric oxide, NacNacGa(O), which can easily cleave the C?H bonds of aliphatic and aromatic substrates featuring good donor sites. The products of this reaction are gallium organyl hydroxides. DFT calculations show that these reactions start with the formation of NacNac‐Ga(O)(L) adducts, the oxo ligand of which can easily abstract protons from nearby C?H bonds, even for sp2‐hybridized carbon centers. Aliphatic amines do not enter this reaction for kinetic reasons, presumably because of the unfavorable sterics. 相似文献
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Sergio Fernndez Jairo Gonzlez Javier Santamaría Alfredo Ballesteros 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(31):10813-10817
Reported herein is the isolation and characterization, for the first time, of a σ‐gold allenyl complex as an intermediate in gold catalysis. This intermediate was captured during the study of a novel gold(I)‐catalyzed propargylation of carbonyl compounds with propargylsilanes. Notably, the gold‐catalyzed propargylation reaction, which proceeds with aldehydes and ketones, can be driven to the formation of either homopropargyl silyl ethers or the in situ synthesis of corresponding 2‐silyl‐4,5‐dihydrofurans. 相似文献
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