Dinitrogen reduction via photochemical activation of heteroleptic tris(cyclopentadienyl) rare-earth complexes

Dinitrogen can be reduced by photochemical activation of the Ln(3+) mixed-ligand tris(cyclopentadienyl) rare-earth complexes (η(5)-C5Me5)(3-x)(C5Me4H)(x)Ln (Ln = Y, Lu, Dy; x = 1, 2). [(C5Me4R)2Ln]2(μ-η(2):η(2)-N2) products (R = H, Me) are formed in reactions in which N2 is reduced to (N═N)(2-) and (C5Me4H)(-) is oxidized to (C5Me4H)2. Density functional theory indicates that this unusual example of rare-earth photochemistry can be rationalized by absorptions involving the (η(3)-C5Me4H)(-) ligands.