MAu₂GeS₄-Chalcogel (M = Co, Ni): Heterogeneous Intra- and Intermolecular Hydroamination Catalysts

High surface area macroporous chalcogenide aerogels (chalcogels) MAu₂GeS₄ (M = Co, Ni) were prepared from K₂Au₂GeS₄ precursor and Co(OAc)₂ or NiCl₂ by one-pot sol-gel metathesis reactions in aqueous media. The MAu₂GeS₄-chalcogels were screened for catalytic intramolecular hydroamination of 4-pentyn-1-amine substrate at different temperatures. 87% and 58% conversion was achieved at 100 °C, using CoAu₂GeS₄- and NiAu₂GeS₄-chalcogels respectively, and the reaction kinetics follows the first order. It was established that the catalytic performance of the aerogels is associated with the M²⁺ centers present in the structure. Intermolecular hydroamination of aniline with 1-R-4-ethynylbenzene (R = -H, -OCH₃, -Br, -F) was carried out at 100 °C using CoAu₂GeS₄-chalcogel catalyst, due to its promising catalytic performance. The CoAu₂GeS₄-chalcogel regioselectively converted the pair of substrates to respective Markovnikov products, (E)-1-(4-R-phenyl)-N-phenylethan-1-imine, with 38% to 60% conversion.