Diiron dithiolate complexes have received special attention because of their structural similarity to the active site of [FeFe]-hydrogenases, which are the most efficient and fastest catalysts for the generation of dihydrogen in nature. Recently, we established a novel and efficient way to prepare phosphinesubstituted diiron aza-and oxadithiolate complexes. Reaction of Fe 2 (μ-SCH 2 OH) 2 (CO) 6 and several phosphine ligands L (L = PPh 3 , PPh 2 (2-C 5 H 4 N), P(C 6 H 4 -4-CH 3 ) 3 ) affords the intermediate Fe 2 (μ-SCH 2 OH) 2 (CO) 5 L, while the intermediate in situ reacts with primary amines RNH 25 [PPh 2 (2-C 5 H 4 N)] (5), Fe 2 [(μ-SCH 2 ) 2 NCH 2 CH 2 CH 2 SCH 3 ](CO) 5 [P(C 6 H 4 -4-CH 3 ) 3 ] (6), Fe 2 [(μ-SCH 2 ) 2 N C 6 H 4 -4-CH 3 ](CO) 5 [PPh 2 (2-C 5 H 4 N)] (7), and Fe 2 [(μ-SCH 2 ) 2 N C 6 H 4 -4-CH 3 ](CO) 5 [P(C 6 H 4 -4-CH 3 ) 3 ] (8) in moderate yields. A novel complex Fe 2 [(μ-SCH 2 ) 2 NCH 2 CH 2 PPh 2 ](CO) 5 (9) can be obtained by reaction of Fe 2 (μ-SCH 2 OH) 2 (CO) 6 and Ph 2 PCH 2 CH 2 NH 2 . In addition, according to the same strategy, phosphine-substituted diiron oxadithiolate complexes Fe 2 [(μ-SCH 2 ) 2 O](CO) 5 [P(C 6 H 4 -4-F) 3 ] (10), Fe 2 [(μ-SCH 2 ) 2 O](CO) 5 [P(C 6 H 4 -4-CH 3 ) 3 ] (11), and Fe 2 [(μ-SCH 2 ) 2 O](CO) 5 (Ph 2 PCH 2 CH 3 ) ( 12) have been successfully synthesized. All of the new complexes 1−12 were fully characterized by elemental analysis, IR, and NMR spectroscopy, and particularly for 1−4, 6, 7, and 9−11 by X-ray single diffraction analysis. Moreover, complexes 1 and 10 were found to be catalysts for H 2 production under electrochemical conditions.

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Acylhydrazones formation has been widely applied in materials science and biolabeling. However, their sluggish condensation rate under neutral conditions limits its application. Herein, indolines with electron-donating groups are reported as a new catalyst scaffold, which can catalyze acylhydrazone, hydrazone, and oxime formation via an iminium ion intermediate. This new type of catalyst showed up to 15-fold rate enhancement over the traditional anilinecatalyzed reaction at neutral conditions. The identified indoline catalyst was successfully applied in hydrogel formation.Letter pubs.acs.org/OrgLett

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Zinc or swim: Arylation of benzyl trifluoroacetates with arylzinc reagents in the presence of β‐hydrogen atoms were realized under mild conditions. Both electron‐rich and electron‐deficient arene substrates were successfully arylated. This arylation method could offer a very versatile synthetic route to access a series of diversity‐oriented diarylalkane motifs. TFA = trifluoroacetyl.