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

The catalytic hydrogen-isotope exchange (HIE) of unactivated C(sp³)─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(CH₂tBu)₂(μ-CHtBu)₂CoCp*], 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 D₂, 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 D₂ 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.