Sipyagina Nataliya A, Vlasenko Nikita E, Malkova Alena N, Kopitsa Gennady P, Gorshkova Yulia E, Kottsov Sergey Yu, Lermontov Sergey A
Institute of Physiologically Active Compounds of Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry of the Russian Academy of Sciences, 1 Severnij pr., Chernogolovka 142432, Russia.
Institute of Silicate Chemistry of Russian Academy of Sciences, 2 Adm. Makarova nab., St. Petersburg 199155, Russia.
Molecules. 2024 Apr 19;29(8):1868. doi: 10.3390/molecules29081868.
A series of silica-based aerogels comprising novel bifunctional chelating ligands was prepared. To produce target aerogels, two aminosilanes, namely (3-aminopropyl)trimethoxysilane (APTMS) and -(2-aminoethyl)-3-aminopropyltrimethoxysilane (AEAPTMS), were acylated by natural amino acids (()-(+)-2-phenylglycine or -phenylalanine), followed by gelation and supercritical drying (SCD). Lithium tetrachloropalladate was used as the metal ion source to prepare strong complexes of Pd with amino acids covalently bonded to a silica matrix. Aerogels bearing chelate complexes retain the Pd oxidation state after supercritical drying in CO, but the Pd ion is reduced to Pd metal after SCD in isopropanol. Depending on the structure of amino complexes, Pd-containing aerogels showed catalytic activity and selectivity in the hydrogenation reactions of C=C, C≡C and C=O bonds.
制备了一系列包含新型双功能螯合配体的二氧化硅基气凝胶。为了制备目标气凝胶,两种氨基硅烷,即(3-氨基丙基)三甲氧基硅烷(APTMS)和 -(2-氨基乙基)-3-氨基丙基三甲氧基硅烷(AEAPTMS),被天然氨基酸(()-(+)-2-苯基甘氨酸或 - 苯丙氨酸)酰化,然后进行凝胶化和超临界干燥(SCD)。四氯钯酸锂用作金属离子源,以制备与共价键合到二氧化硅基质上的氨基酸形成的强钯配合物。带有螯合配合物的气凝胶在 CO 中进行超临界干燥后保持钯的氧化态,但在异丙醇中进行 SCD 后钯离子被还原为钯金属。根据氨基配合物的结构,含钯气凝胶在 C = C、C≡C 和 C = O 键的氢化反应中表现出催化活性和选择性。