Munir Talha, Aneggi Eleonora, Baratta Walter, Genesin Leonardo, Zuccaccia Daniele, Trigatti Fabio
Dipartimento di Scienze Agroalimentari, Ambientali e Animali, Sezione di Chimica, Università di Udine, Via Cotonificio 108, Udine, I-33100, Italy.
Dipartimento di Scienze della Vita, Università di Trieste, Via Weiss 2, Trieste, 34128, Italy.
Chemistry. 2025 Jul 8;31(38):e202501214. doi: 10.1002/chem.202501214. Epub 2025 Jun 23.
2,2'-bipyridine is considered to be the most widely used chelating ligand and it has been extensively studied especially in the areas of coordination chemistry, medicine, materials, and catalysis. A mechanochemical reaction is a process that involves the application of mechanical energy and it provides a high yield in a shorter reaction time and eliminates the need for bulk solvents, typically request in solvothermal reaction. Notwithstanding the importance of the synthesis of bipyridine-metal compounds for several decades and recent advancements in the mechanochemical synthesis the development of a mechanochemical protocol for the synthesis of metal complexes bearing bipyridine remains unexplored. In this work, we extensively studied the mechanochemistry reaction of more than 10 metallic precursors of Ru, Ir, Pt, Pd, Fe, and Co with 2,2'-bipyridine in different stoichiometric ratio without utilization of bulk solvents, under ambient conditions and without air-sensitive procedures. A comparison of the yield, reaction time, temperature, frequency, green metrics (E-factor and the Effective Mass Yield (EMY)) of conventional solvothermal methodologies and mechanochemical synthesis clearly indicates that the mechanochemical approach is more sustainable and efficient. Mechanochemistry approach can be complementary to common solvothermal approach, and in the future, it will be required greater attention in the field of organometallic chemistry.
2,2'-联吡啶被认为是应用最为广泛的螯合配体,尤其在配位化学、医学、材料和催化等领域得到了广泛研究。机械化学反应是一个涉及机械能应用的过程,它能在较短的反应时间内提供高产率,并且无需大量溶剂,而溶剂热反应通常需要大量溶剂。尽管几十年来联吡啶金属化合物的合成具有重要意义,且机械化学合成也有了最新进展,但用于合成含联吡啶金属配合物的机械化学方法仍未得到探索。在这项工作中,我们在环境条件下且无需空气敏感操作的情况下,广泛研究了钌、铱、铂、钯、铁和钴的10多种金属前体与2,2'-联吡啶以不同化学计量比进行的机械化学反应,且未使用大量溶剂。常规溶剂热方法与机械化学合成在产率、反应时间、温度、频率、绿色指标(E因子和有效质量产率(EMY))方面的比较清楚地表明,机械化学方法更具可持续性和高效性。机械化学方法可以作为常见溶剂热方法的补充,并且在未来,有机金属化学领域将需要对其给予更多关注。