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High-valent cerium complexes of alkyl and benzyl ligands are unprecedented due to the incompatibility of the typically highly oxidizing Ce4+ion and the reducing alkyl or benzyl ligand. Herein we report the synthesis and isolation of the first tetravalent cerium alkyl and benzyl complexes supported by the tri-tert-butyl imidophosphorane ligand, [NP(tBu)3]1–. The Ce4+monoiodide complex, [Ce4+I(NP(tert-butyl)3)3] (1-CeI), serves as a precursor to the alkyl and benzyl complexes, [Ce4+(Npt)(NP(tert-butyl)3)3] (2-CeNpt) (Npt = neopentyl, CH2C(CH3)3) and [Ce4+(Bn)(NP(tert-butyl)3)3] (2-CeBn) (Bn = benzyl, CH2Ph). The bonding and structure of these complexes are characterized by single-crystal XRD, NMR and UV–vis–NIR spectroscopy, cyclic voltammetry, and DFT studies.

This study provides atomistic insights into the interface between a single-site catalyst and a transition metal chalcogenide support and reveals that peak catalytic activity occurs when edge/support redox cooperativity is maximized. A molecular platform MCo6Se8(PEt3)4(L)2(1-M, M = Cr, Mn, Fe, Co, Cu, and Zn) was designed in which the active site (M)/support (Co6Se8) interactions are interrogated by systematically probing the electronic and structural changes that occur as the identity of the metal varies. All 3d transition metal 1-M clusters display remarkable catalytic activity for coupling tosyl azide and tert-butyl isocyanide, with Mn and Co derivatives showing the fastest turnover in the series. Structural, electronic, and magnetic characterization of the clusters was performed using single crystal X-ray diffraction, 1H and 31P nuclear magnetic resonance spectroscopy, electronic absorption spectroscopy, cyclic voltammetry, and computational methods. Distinct metal/support redox regimes can be accessed in 1-M based on the energy of the edge metal’s frontier orbitals with respect to those of the cluster support. As the degree of electronic interaction between the edge and the support increases, a cooperative regime is reached wherein the support can deliver electrons to the catalytic site, increasing the reactivity of key metal-nitrenoid intermediates.