Radium Revisited: Revitalization of the Coordination Chemistry of Nature’s Largest +2 Cation
Zhuanling Bai, Jacob P. Brannon, Cristian Celis‐Barros, Nicholas Beck, Joseph M. Sperling, Brian M. Rotermund, Daniela Gomez Martinez, Hannah B. Wineinger, Thomas E. Albrecht‐Schmitt
Abstract
The crystallization, single crystal structure, and Raman spectroscopy of Ra(NO 3 ) 2 have been investigated by experimentation and theory, which represent the first pure radium compound characterized by single crystal X-ray diffraction. The Ra 2+ centers are bound by six chelating nitrate anions to form an anticuboctahedral geometry. The Raman spectrum acquired from a single crystal of Ra(NO 3 ) 2 generally occurs at a lower frequency than found in Ba(NO 3 ) 2, as expected. Computational studies on Ra(NO 3 ) 2 provide an estimation of the bond orders via Wiberg bond indices and indicate that Ra–O interactions are weak with values of 0.025 and 0.026 for Ra–O bonds. Inspection of natural bond orbitals and natural localized molecular orbitals suggest negligible orbital mixing. However, second-order perturbation interactions show that donation from the lone pairs of the nitrate oxygen atoms to the 7s orbitals of Ra 2+ stabilizes each Ra–O interaction by ca . 5 kcal mol –1 .