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meta-Directing Deactivators: –NO2, –CN, –CHO, –⁠CO2R, –COR, –CO2H01:13

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All meta-directing substituents are deactivating groups. These substituents withdraw electrons from the aromatic ring, making the ring less reactive toward electrophilic substitution. For example, the nitration of nitrobenzene is 100,000 times slower than that of benzene because of the deactivating effect of the nitro group. The first step in an electrophilic aromatic substitution is the addition of an electrophile to form a resonance-stabilized carbocation. The energy diagrams for...
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Secondary amines react with nitrous acid to form N-nitrosamines, as depicted in Figure 1. Nitrous acid, a weak and unstable acid, is formed in situ from an aqueous solution of sodium nitrite and strong acids, such as hydrochloric acid or sulfuric acid, in cold conditions. In the presence of an acid, the nitrous acid gets protonated. The subsequent loss of water results in the formation of the electrophile known as nitrosonium ion.
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Kinetic Studies and Significance
In a chemical reaction, a relationship exists between the concentration of reactants and the rate at which the reaction proceeds. The study to measure this relationship is known as the kinetics of a chemical reaction. Kinetic studies are used to deduce the rate law of a chemical reaction, which provides information about the species involved during the transition state of the rate-determining step. Thus, kinetic studies help to derive the mechanism of a...
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The kinetic studies of SN2 reactions suggest an essential feature of its mechanism: it is a single-step process without intermediates. Here, both the nucleophile and the substrate participate in the rate-determining step.
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An SN2 reaction of an alkyl halide is a single-step process in which bond formation between the nucleophile and the substrate and bond breaking between the substrate and the halide occurs simultaneously through a transition state without forming an intermediate.
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In an SN2 reaction, the nucleophilic attack on the substrate and departure of the leaving group occurs simultaneously through a transition state. As the nucleophile approaches the substrate from the back-side, the configuration of the substrate carbon changes from tetrahedral to trigonal bipyramidal and then back to tetrahedral, leading to an inversion in the configuration of the product.
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Trapping CS22- and S32- between Two Ytterbium Formamidinates.

Daniel Werner1, Glen B Deacon1, Peter C Junk2

  • 1School of Chemistry , Monash University , Clayton , Victoria 3800 , Australia.

Inorganic Chemistry
|January 23, 2019
PubMed
Summary

Researchers synthesized novel ytterbium (Yb) complexes. Treatment of Yb(II) precursors with carbon disulfide (CS2) or sulfur (S8) yielded Yb(III) complexes, including a rare-earth trisulfide compound.

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Area of Science:

  • Organometallic Chemistry
  • Inorganic Chemistry
  • Rare-Earth Chemistry

Background:

  • Ytterbium(II) complexes with formamidinate ligands are known precursors.
  • Reactions with sulfur-containing reagents can lead to diverse inorganic products.

Purpose of the Study:

  • To investigate the reactivity of Yb(II) complexes with carbon disulfide (CS2) and elemental sulfur (S8).
  • To characterize the resulting ytterbium(III) complexes and their unique sulfur-containing moieties.

Main Methods:

  • Synthesis of ytterbium(II) precursors [Yb(DippForm)2(thf)n].
  • Reaction of precursors with excess CS2 or S8.
  • Crystallographic characterization of the resulting Yb(III) complexes.

Main Results:

  • Formation of [YbIII2(DippForm)4(CS2)], a novel compound featuring the CS2(2-) dianion.
  • Isolation and characterization of [YbIII2(DippForm)4(S2)0.5/(S3)0.5], the first crystallographically defined rare-earth trisulfide complex.
  • The reactions demonstrate controlled sulfur incorporation into ytterbium coordination spheres.

Conclusions:

  • Yb(II) formamidinate complexes can be effectively transformed into Yb(III) complexes with unique sulfur ligands.
  • The study expands the known chemistry of ytterbium with sulfur, highlighting the CS2(2-) dianion and rare-earth trisulfide complexes.