Lachguar Abdelhak, Neumann Till, Pichugov Andrey V, Jeanneau Erwann, Veyre Laurent, Thieuleux Chloé, Camp Clément
Laboratory of Catalysis, Polymerization, Processes and Materials (CP2 M UMR 5128), CNRS, Universite Claude Bernard Lyon 1, CPE-Lyon, Institut de Chimie de Lyon, 43 Bd du 11 Novembre 1918, F-69616 Villeurbanne, France.
Centre de Diffractométrie Henri Longchambon, Universite Claude Bernard Lyon 1, 5 Rue de la Doua, 69100 Villeurbanne, France.
Dalton Trans. 2025 Feb 25;54(9):3804-3811. doi: 10.1039/d4dt03171g.
Metal-catalyzed hydrogen isotope exchange (HIE) has become a valuable method for incorporating deuterium and tritium into organic molecules, with applications in a wide range of scientific fields. This study explores the role of transition metal cooperativity in enhancing catalytic hydrogen/deuterium (H/D) exchange using early-late heterobimetallic polyhydride (ELHB) complexes. A series of four ELHB complexes, of general formula [M(CHBu)(H)M'Cp*], combining early transition metals (M = Hf, Ta) with late metals (M' = Ir, Os), were synthesized and evaluated for their catalytic activity in HIE of (hetero)arenes. Hafnium-iridium and hafnium-osmium complexes showed a clear improvement in catalytic efficiency and reaction rate over monometallic analogues, suggestive of metal-metal synergy. Conversely, the tantalum-based heterobimetallic complexes showed lower catalytic performance, revealing that not all metal combinations are equally effective. These results underline the importance of careful metal selection to optimize transition metal cooperativity, and open up new possibilities for the design of more efficient H/D exchange catalysts.
金属催化氢同位素交换（HIE）已成为一种将氘和氚引入有机分子的重要方法，在广泛的科学领域都有应用。本研究探讨了早期-晚期异双金属多氢化物（ELHB）配合物中过渡金属协同作用在增强催化氢/氘（H/D）交换方面的作用。合成了一系列通式为[M(CHBu)(H)M'Cp*]的四种ELHB配合物，它们将早期过渡金属（M = Hf、Ta）与晚期金属（M' = Ir、Os）结合起来，并评估了它们在（杂）芳烃HIE中的催化活性。铪-铱和铪-锇配合物在催化效率和反应速率方面比单金属类似物有明显提高，表明存在金属-金属协同作用。相反，基于钽的异双金属配合物表现出较低的催化性能，这表明并非所有金属组合都同样有效。这些结果强调了谨慎选择金属以优化过渡金属协同作用的重要性，并为设计更高效的H/D交换催化剂开辟了新的可能性。
