Recent experiments demonstrate that the lanthanides have an active reduction chemistry with species such as N2, NO, CO and CO2, and that complexes of unprecedented radical species, such as (N2)3- and (NO)2- can be isolated.1, 2 To elucidate the nature of the metal valence orbitals involved in these reactions and products, density functional theory calculations were performed for a series of La, Ce, Sm, Dy, Ho, Er, and Y compounds. We present results for structures, IR spectra, and UV/Vis spectra all indicating the 5d orbitals play a much larger role in the reduction chemistry of rare-earth compounds than previously expected. In particular, we report computational studies on the first molecular examples of Ho(II) and Er(II), as well as photochemically active [C5Me5]2(C4Me4H)Ln complexes.?1 Evans, W. J. et al. Nature Chemistry 2010  , 2, 644-7.?2 Fang, M. et al. Journal of the American Chemical Society 2011  , 133, 3784-3787.

Computational studies of unexpected 5d rare-earth metal reduction chemistry

244th National Meeting (2012)

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