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Herein, we have reported a new series of NNS-donor ligands coordinated Ni(II) complexes and utilized them as catalytic activator to synthesize N-alkylated amines and 1,2-disubstituted benzimidazoles. The reaction of thiophenol/4-chlorothiophenol/4-methylthiophenol/4-methoxythiophenol with 2-bromo-N-quinolin-8-yl-acetamide in presence of sodium hydroxide in ethanol at 80 °C gave [C 9 H 6 N-NH-C(O)-CH 2 -S-Ar] [Ar=C 6 H 5 (L1); C 6 H 4 Cl-4 (L2); C 6 H 4 Me-4 (L3) and C 6 H 4 -OMe-4 (L4)], respectively. The corresponding reaction of L1-L4 with Ni(OAc) 2 in methanol at 80 °C for 3 hours resulted in octahedral nickel complexes [(L1-H) 2 Ni] (C1), [(L2-H) 2 Ni] (C2), [(L3-H) 2 Ni] (C3), and [(L4-H) 2 Ni] (C4), respectively. All compounds have been characterized by micro and spectroscopic analysis. The molecular structure of complexes C1-C3 has also been determined by single crystal X-ray diffraction data. The utility of complexes C1-C4 were evaluated for the N-alkylation of aniline with benzyl alcohols, and for 1,2-disubstituted benzimidazoles synthesis. The obtained results indicate that complex C1 showed better catalytic activity in both N-alkylation of amines with benzyl alcohols [catalyst loading: 2.0 mol %; Yield up to 92 %], and for 1,2-disubstituted benzimidazoles derivatives [catalyst loading: 2.0 mol %; Yield up to 94 %)]. The mechanistic studies suggested that the reaction works through hydrogen borrowing from benzyl alcohol and its subsequent utilization for in situ reduction of imine. The experimentally observed catalytic reactivity patterns of complexes C1-C4 have found in good agreement with the HOMO-LUMO energy gaps obtained by DFT analysis of corresponding complexes., (© 2024 Wiley-VCH GmbH.)

An air-stable, inexpensive, and isolable cobalt(II) complex (C1) of N-((1-methyl-1H-imidazol-2-yl)methyl)-2-(phenylselanyl)ethan amine (L1) was synthesized and characterized. The complex was used to catalyze a one-pot cascade reaction between 2-(2-aminophenyl)ethanols and benzyl alcohol derivatives. Interestingly, 2-aryl-3-formylindole derivatives were formed instead of N-alkylated or C-3 alkylated indoles. A broad substrate scope can be activated using this protocol with only 5.0 mol % catalyst loading to achieve up to 87 % yield of 2-aryl-3-formylindole derivatives. The mechanistic studies suggested that the reaction proceeds through tandem imine formation followed by cyclization., (© 2024 Wiley-VCH GmbH.)

Herein, we have reported the synthesis of a macrocyclic organosulfur ligand (L1) having a seventeen-membered macrocyclic ring. Subsequently, the corresponding trans-palladium complex (C1) of bulky macrocyclic organosulfur ligand (L1) was synthesized by reacting it with PdCl 2 (CH 3 CN) 2 salt. The newly synthesized ligand and complex were characterized using various analytical and spectroscopic techniques. The complex showed a square planar geometry with trans orientation of two ligands around the palladium center. The complex possesses intramolecular SCH…Cl interactions of 2.648 Å between the macrocyclic ligand and palladium dichloride. The potential energy surface (PES) for the rotational process of C1 suggested a barrier of ~23.81 kcal/mol for chlorine rotation. Furthermore, the bulky macrocyclic organosulfur ligand stabilized palladium complex (C1) was used as a catalyst (2.5 mol %) for α-olefination of nitriles by primary alcohols. The α,β-unsaturated nitrile compounds were found to be the major product of the reaction (57-78 % yield) with broad substrate scope and large functional group tolerance. Notably, the saturated nitrile product was not observed during the reaction. The mechanistic studies suggested the formation of H 2 and H 2 O as only by-products of the reaction, thereby making the protocol greener and sustainable., (© 2023 Wiley-VCH GmbH.)