Reversible sigma C-C bond formation between phenanthroline ligands activated by (C5Me5)2Yb.

The electronic structure and associated magnetic properties of the 1,10-phenanthroline adducts of Cp*2Yb are dramatically different from those of the 2,2'-bipyridine adducts. The monomeric phenanthroline adducts are ground state triplets that are based upon trivalent Yb(III), f(13), and (phen(•-) ) that are only weakly exchange coupled, which is in contrast to the bipyridine adducts whose ground states are multiconfigurational, open-shell singlets in which ytterbium is intermediate valent ( J. Am. Chem. Soc 2009 , 131 , 6480 ; J. Am. Chem. Soc 2010 , 132 , 17537 ). The origin of these different physical properties is traced to the number and symmetry of the LUMO and LUMO+1 of the heterocyclic diimine ligands. The bipy(•-) has only one π*1 orbital of b1 symmetry of accessible energy, but phen(•-) has two π* orbitals of b1 and a2 symmetry that are energetically accessible. The carbon pπ-orbitals have different nodal properties and coefficients and their energies, and therefore their populations change depending on the position and number of methyl substitutions on the ring. A chemical ramification of the change in electronic structure is that Cp*2Yb(phen) is a dimer when crystallized from toluene solution, but a monomer when sublimed at 180-190 °C. When 3,8-Me2phenanthroline is used, the adduct Cp*2Yb(3,8-Me2phen) exists in the solution in a dimer-monomer equilibrium in which ΔG is near zero. The adducts with 3-Me, 4-Me, 5-Me, 3,8-Me2, and 5,6-Me2-phenanthroline are isolated and characterized by solid state X-ray crystallography, magnetic susceptibility and LIII-edge XANES spectroscopy as a function of temperature and variable-temperature (1)H NMR spectroscopy.