Abstract:
Multinuclear complexes are metal compounds featured by adjacent bound metal centers that can lead to unconventional reactivity. Some M2L4-type paddlewheel dinuclear complexes with monoanionic bridging ligands feature promising properties, including therapeutic ones. Molybdenum has been studied for the formation of multiple-bonded M2+ compounds due to their unique scaffold, redox, and spectroscopic properties as well as for applications in several fields including catalysis and biology. These latter are much less explored and only sporadic studies have been carried out. Here, a series of four dimolybdenum (II,II) carboxylate paddlewheel complexes were synthesized using different Non-Steroidal Anti-Inflammatory Drugs (NSAIDs) as ligands. The reaction of (NH4)5[Mo2Cl9]·H2O with the selected NSAIDs in methanol produced the complexes Mo2(μ-O2CR)4 where RCO2 is ibuprofen (1), naproxen (2), aspirin (3) and indomethacin (4). The products were obtained in good yields and extensively characterized with integrated techniques. Stability and solution behaviour were studied using a mixed experimental and computational approach. Finally, the biological activity of 1 and 3 (i.e. the most reactive and the most stable compounds of the series, respectively) was preliminarily assessed confirming the disassembling of the molecules in the biological milieu. Overall, some very interesting results emerged for these unconventional compounds from a mechanistic point of view.
摘要:
多核络合物是金属化合物,其特征在于可导致非常规反应性的相邻结合金属中心。某些具有单阴离子桥接配体的M2L4型桨轮双核配合物具有很好的性能,包括治疗性的。由于其独特的支架,钼已被研究用于形成多重键合的M2+化合物,氧化还原,和光谱特性以及在催化和生物学等多个领域的应用。后者的探索要少得多,只进行了零星的研究。这里,一系列四双钼(II,II)使用不同的非甾体抗炎药(NSAID)作为配体合成羧酸桨轮配合物。(NH4)5[Mo2Cl9]·H2O与所选NSAIDs在甲醇中的反应产生了配合物Mo2(μ-O2CR)4,其中RCO2是布洛芬(1),萘普生(2),阿司匹林(3)和吲哚美辛(4)。以良好的收率获得产物,并用综合技术广泛表征。使用混合的实验和计算方法研究了稳定性和溶液行为。最后,1和3的生物活性(即系列中最具反应性和最稳定的化合物,分别)进行了初步评估,以确认分子在生物环境中的分解。总的来说,从机械的角度来看,这些非常规化合物出现了一些非常有趣的结果。