Coordination of Lanthanide Nitrates with N,N,N',N'-Tetramethylsuccinamide.
Two compound classes have been identified from the reaction of trivalent lanthanide nitrates with tetramethylsuccinamide (TMSA). The nature of these Ln-TMSA compounds has been examined in the solid phase by thermogravimetric analysis (TGA) and single-crystal X-ray diffraction and in solution by infrared spectroscopy. Isostructural, 10-coordinate compounds with a 2:1 TMSA:Ln stoichiometry were found for the lanthanides La and Ce. Single-crystal X-ray diffraction analysis of the Ln-TMSA nitrate compounds, Ln = La and Ce, reveals a polymeric structure with each metal center containing one chelating bidentate succinamide and two bridging bidentate succinamides. For the remaining lanthanides Pr, Nd, Gd, Yb, and Lu, a series of isostructural, 9-coordinate compounds containing a 3:2 TMSA:Ln ratio were formed. Single-crystal X-ray diffraction analysis of the Ln-TMSA products, Ln = Ce, Pr, Nd, Gd, and Yb, reveals these compounds to be dimeric, with each metal center containing one chelating bidentate succinamide and two bridging bidentate succinamides. The solution stoichiometries were examined in acetonitrile-water mixtures and support the stoichiometries observed in the solid-state structures. Cerium nitrate appears to be a special (and transitional) lanthanide in its reaction with TMSA. Although infrared and TGA analyses indicate a 2:1 ligand-to-metal product, crystals for both the 2:1 and 3:2 compounds were isolated. No evidence for such multiple forms was found with any of the other lanthanides.
Rapko
Brian M.
BM
Pacific Northwest National Laboratory, Richland, Washington 99352, and Department of Chemistry, The University of Alabama, Tuscaloosa, Alabama 35487.
McNamara
Bruce K.
BK
Rogers
Robin D.
RD
Lumetta
Gregg J.
GJ
Hay
Benjamin P.
BP