Synthesis of Perdeuterated Pentane and THF Under Mild Conditions by Silica‐Supported Ta/M (M = Co, Ir) Heterobimetallic Catalysts

Abstract The catalytic hydrogen‐isotope exchange (HIE) of unactivated C(sp 3 )─H bonds remains a formidable challenge, relevant for the synthesis of high‐purity high‐value perdeuterated NMR solvents such as pentane or tetrahydrofuran. Existing methods primarily rely on precious metal‐based catalysts (eg. Ir, Ru) under homogeneous conditions. In pursuit of more sustainable alternatives, we report the synthesis of the heterobimetallic complex [Ta(CH 2 t Bu) 2 (μ‐CH t Bu) 2 CoCp*], 1 , which is used for the preparation of a novel silica‐supported tantalum–cobalt heterobimetallic catalyst through Surface OrganoMetallic Chemistry (SOMC). This Ta/Co material demonstrated exceptional catalytic efficiency in perdeuterating pentane under mild conditions (room temperature, < 1 bar D 2 , 1 mol% cat.), outperforming both the Ta monometallic and the noble‐metal based Ta/Ir heterobimetallic analogues. Furthermore, we took profit of the complementary arene HIE and deuterogenation activities of the Ta/M (M = Ir, Co) catalysts to develop a tandem catalytic synthetic strategy for the efficient preparation of perdeuterated tetrahydrofuran from furan, achieving up to 94% total deuterium incorporation. This novel catalytic system offers several key advantages such as a) mild reaction conditions, b) atom‐efficient use of D 2 as the deuterium source, and c) simplified handling, allowing for the recovery of pure deuterated solvent via simple condensation, not hampered by the use of solvents nor additives.