The Pormylation of an Aromatic Nucleus by the Use of 2-Ethoxy-1,3-dithiolane

Jo, Shigeo; Tanimoto, Shigeo; Sugimoto, Toyonari; Okano, Masaya

doi:10.1246/bcsj.54.2120

Cited by 13 publications

(2 citation statements)

References 10 publications

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“…Yet the robust chelation between thiol and Ni II sites gives undesirable Ni 3 complex (Figure S11) and prevents the occurrence of thioacetal reactions. Therefore, a pre‐reaction route to obtain the thioacetal ligand is essential [39] . 2‐Ln were obtained from 1‐Ln via a structural transformation mediated by in situ thioacetal ligand substitution (Method 1) or synthesized by using a one‐pot reaction (Method 2, Figure 1B and see Supplemental Information for more details).…”

Section: Resultsmentioning

confidence: 99%

“…Therefore, a pre-reaction route to obtain the thioacetal ligand is essential. [39] 2-Ln were obtained from 1-Ln via a structural transformation mediated by in situ thioacetal ligand substitution (Method 1) or synthesized by using a one-pot reaction (Method 2, Figure 1B and see Supplemental Information for more details).…”

Section: Structural Analysis and Transformationmentioning

confidence: 99%

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Spin‐State Control in Dysprosium(III) Metallacrown Magnets via Thioacetal Modification

Deng,

Wu,

Ruan

et al. 2024

Angewandte Chemie

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Integrating controllable spin states into single‐molecule magnets (SMMs) enables precise manipulation of magnetic interactions at a molecular level, but remains a synthetic challenge. Herein, we developed a 3d‐4f metallacrown (MC) magnet [DyNi5(quinha)5(Clsal)2(py)8](ClO4)∙4H2O (H2quinha = quinaldichydroxamic acid, HClsal = 5‐chlorosalicylaldehyde) wherein a square planar NiII is stabilized by chemical stacking. Thioacetal modification was employed via post‐synthetic ligand substitutions and yielded [DyNi5(quinha)5(Clsaldt)2(py)8](ClO4)·3H2O (HClsaldt = 4‐chloro‐2‐(1,3‐dithiolan‐2‐yl)phenol). Thanks to the additional ligations of thioacetal onto the NiII site, coordination‐induced spin state switching (CISSS) took place with spin state altering from low‐spin S = 0 to high‐spin S = 1. The synergy of CISSS effect and magnetic interactions results in distinct energy splitting and magnetic dynamics. Magnetic studies indicate prominent enhancement of reversal barrier from 57 cm−1 to 423 cm−1, along with hysteresis opening and an over 200‐fold increment in coercive field at 2 K. Ab initio calculations provide deeper insights into the exchange models and rationalize the relaxation/tunnelling pathways. These results demonstrate here provide a fire‐new perspective in modulating the magnetization relaxation via the incorporation of controllable spin states and magnetic interactions facilitated by the CISSS approach.

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Section: Resultsmentioning

confidence: 99%

Section: Structural Analysis and Transformationmentioning

confidence: 99%

Spin‐State Control in Dysprosium(III) Metallacrown Magnets via Thioacetal Modification

Deng,

Wu,

Ruan

et al. 2024

Angewandte Chemie

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Friedel‐Crafts Reactions

Oláh

Reddy

Prakash

2000

Kirk-Othmer Encyclopedia of Chemical Technology

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After the initial discovery by Friedel and his American associate, James Mason Crafts, that anhydrous aluminum chloride could be used as a condensing agent in a general synthetic method for furnishing an infinite number of hydrocarbons. They extended their discoveries of the catalytic effect of aluminum chloride in a variety of organic reactions: (1) reactions of alkyl and acyl halides and unsaturated compounds with aromatic and aliphatic hydrocarbons; (2) reactions of acid anhydrides with aromatic hydrocarbons; (3) reactions of oxygen, sulfur, sulfur dioxide, carbon dioxide, and phosgene with aromatic hydrocarbons; (4) cracking of aliphatic and aromatic hydrocarbons; and (5) polymerization of unsaturated hydrocarbons. The diversity of reactions is astounding. Many important industrial processes such as the production of high octane gasoline, ethylbenzene (eventually leading to polystyrene), synthetic rubber, plastics, and detergent alkylates are based on Friedel‐Crafts chemistry. Friedel‐Crafts‐type reactions are generally considered to be any substitution, isomerization, elimination, cracking, polymerization, or addition reaction that takes place under the catalytic effect of Lewis acid‐type acidic halides (with or without cocatalysts) or Brønsted acids. Friedel‐Crafts reactions can be divided into two general categories: alkylations and acylations. Within these two broad areas there is considerable diversity. Friedel‐Crafts catalysts are electron acceptors, ie, Lewis acids. Catalysts include acid halides (Lewis acids), metal alkyls and alkoxides, protic acids (Brønsted Acids), acidic oxides and sulfides (acidic chalcogenides), acidic cation‐exchange resins, and superacids (Brønsted superacids, super Lewis acids, Brønsted‐Lewis superacids, solid superacids, and superacidic zeolites).

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