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Relevant academic research and scientific papers

Coinage Metal (Bisfluorosulfonyl)imide Complexes: Preparation, Characterization, and Catalytic Applications

Triflate (–OTf) and triflimide (–NTf2) represent two most widely used weakly coordinating counteranions in transition metal catalysis, yet their high price hinders large-scale application. Herein, we report the preparation, characterization, and catalytic applications of silver(I), gold(I), and copper(II) (bisfluorosulfonyl)imide (–FSI) complexes, showing –FSI as a low cost alternative of –OTf and –NTf2. These complexes, including AgFSI·2MeCN (1), AgFSI·MeCN (2), AgFSI·H2O (3), (AgFSI)6·(H2O)4 (4), AgFSI (5), LAuFSI (6a–6e), and CuFSI2·4H2O (7), are prepared conveniently starting from KFSI, an inexpensive chemical, and shown interesting structural features and some unprecedented coordination modes. In comparison with the corresponding coinage metal triflimides, the FSI complexes have exhibited comparable or better catalytic performance in a series of the model chemical transformations.

Complete Switch of Selectivity in the C-H Alkenylation and Hydroarylation Catalyzed by Iridium: The Role of Directing Groups

A complete switch in the CpIr(III)-catalyzed paths between C-H olefination and hydroarylation was found to be crucially dependent on the type of directing groups. This dichotomy in product distribution was correlated to the efficiency in attaining syn-coplanarity of olefin-inserted 7-membered iridacycles. Theoretical studies support our hypothesis that the degree of flexibility of this key intermediate modulates the β-H elimination, which ultimately affords the observed chemoselectivity.

Reactions and mechanistic studies of rhenium-catalyzed insertion of α,β-unsaturated carbonyl compounds into a C-H bond

A rhenium complex, [ReBr(CO)3(thf)]2, catalyzes the insertion of α, β-unsaturated carbonyl compounds into a C-H bond of aromatic compounds having nitrogen-containing directing groups. In this reaction, Re2(CO)10 can also be used as a catalyst. When imines are employed as the aromatic substrates, sequential cyclization proceeds and indene derivatives are obtained in good to excellent yields. This reactivity is in contrast to those of ruthenium and rhodium complexes, which are usually used as catalysts in the insertion reactions of unsaturated molecules into a C-H bond. Investigations on the reaction mechanism indicate that the rhenium catalyst promotes C-H bond activation of aromatic compounds, the insertion of α, β-unsaturated carbonyl compounds into a Re-C bond, and intramolecular nucleophilic cyclization followed by reductive elimination and the elimination of an amine.