Structural transformation and catalytic hydrogenation activity of amidinate-protected copper hydride clusters

Copper hydrides are important hydrogenation catalysts, but their poor stability hinders the practical applications. Ligand engineering is an effective strategy to tackle this issue. An amidinate ligand, N,N'-Di(5-trifluoromethyl-2-pyridyl)formamidinate (Tf-dpf) with four N-donors has been applied as a protecting agent in the synthesis of stable copper hydride clusters: Cu₁₁H₃(Tf-dpf)₆(OAc)₂ (Cu₁₁) with three interfacial μ₅-H and [Cu₁₂H₃(Tf-dpf)₆(OAc)₂]·OAc (Cu₁₂) with three interstitial μ₆-H. A solvent-triggered reversible interconversion between Cu₁₁ and Cu₁₂ has been observed thanks to the flexibility of Tf-dpf. Cu₁₁ shows high activity in the reduction of 4-nitrophenol to 4-aminophenol, while Cu₁₂ displays very low activity. Deuteration experiments prove that the type of hydride is the key in dictating the catalytic activity, for the interfacial μ₅-H species in Cu₁₁ are involved in the catalytic cycle whereas the interstitial μ₆-H species in Cu₁₂ are not. This work highlights the role of hydrides with regard to catalytic hydrogenation activity.