Data for 'Expanding the Reactivity of Masked Divalent Lanthanide-Isocarbonyl Complexes'

Data for paper published in <i>Organometallics</i><i> </i>2026, 45, 7, 885–891<br><br>CIF and checkcif files for all compounds.<br>IR spectroscopy data for all compounds.NMR spectroscopy data.Magnetic measurements.<b>Abstract</b>Masked divalent reactivity is a potentially powerful strategy for accessing the reducing chemistry of lanthanides without the need to isolate unstable divalent lanthanide compounds. Here, we report the synthesis and characterization of the isocarbonyl-bridged complexes [(Cp*)₂Gd(THF)(u-Fp)]_∞ (<b>1</b>_{<strong>Gd</strong>}) and [(Cp*)₂Lu(μ-Fp)]₂ (<b>1</b>_{<strong>Lu</strong>}) (Fp = CpFe(CO)₂), aiming to extend the masked divalent approach to gadolinium and lutetium, metals with very limited divalent chemistry. Structural studies show that <b>1</b>_{<strong>Gd</strong>} forms as a coordination polymer with nine-coordinate gadolinium centers, whereas <b>1</b>_{<strong>Lu</strong>} is a dimer with eight-coordinate lutetium reflecting the influence of the lanthanide contraction. IR spectroscopy confirms strong isocarbonyl back-bonding in both compounds. Complexes <b>1</b>_{<strong>M</strong>} (M = Gd, Dy, Lu) react with phenazine to afford dimetallic phenazine-bridged products [{(Cp*)₂M}₂(μ-phnz)] (<b>2</b>_{<strong>M</strong>}), demonstrating two-electron reduction of an <i>N</i>-heterocyclic substrate by the isocarbonyl-bridged complexes. Magnetic measurements reveal extremely weak antiferromagnetic exchange in <b>1</b>_{<strong>Gd</strong>} and <b>2</b>_{<strong>Gd</strong>}, while the dysprosium analogue exhibits slow magnetic relaxation governed by Raman and quantum tunnelling processes. These results establish isocarbonyl-bridged lanthanide metallocenes as platforms for ligand-based reduction chemistry involving metals with very limited divalent chemistry.