Carbon-Hydrogen Bond Breaking and Making in the Open-Shell Singlet Molecule Cp* 2 Yb(4,7-Me 2 phen)

The adducts formed between the 4,7-Me2-, 3,4,7,8-Me4-, and 3,4,5,6,7,8-Me6-phenanthroline ligands and Cp*2Yb are shown to have open-shell singlet ground states by magnetic susceptibility and LIII-edge XANES spectroscopy. Variable-temperature XANES data show that two singlet states are occupied in each adduct that are fit to a Boltzmann distribution for which ΔH = 5.75 kJ mol–1 for the 4,7-Me2phen adduct. The results of a CASSCF calculation for the 4,7-Me2phen adduct indicates that three open-shell singlet states, SS1–SS3, lie 0.44, 0.06. and 0.02 eV, respectively, below the triplet state. These results are in dramatic contrast to those acquired for the phenanthroline and 5,6-Me2phen adducts, which are ground state triplets (J. Am. Chem. Soc. 2014, 136, 8626). A model that accounts for these differences is traced to the relative energies of the LUMO and LUMO+1 orbitals that depend on the position the methyl group occupies in the phenanthroline ligand. The model also accounts for the difference in reactivit...