Covalency is a fundamental concept in chemistry used to describe chemical bonding in s-, p-, d-, and f-block elements. Recently, we have made use of Cl K-edge X-ray absorption spectroscopy (XAS) and time-dependent density functional theory (TDDFT) to evaluate covalency in Ln–Cl (Ln = lanthanide) bonds of Oh-LnCl6x- (LnIII = Ce, Nd, Sm, Eu, Gd; LnIV = Ce) anions. The results have been evaluated as a function of (1) the lanthanide metal identity, which was varied across the series, and (2) the lanthanide oxidation state (when practical, i.e. formally CeIII and CeIV). Our unexpected observation of lanthanide 4f- and 5d-orbital participation in covalent bonding will be presented in the context of recent studies on both tetravalent transition metal and actinide hexahalides, MCl62- (M = Ti, Zr, Hf, U, Pu).

Covalency in lanthanides

249th National Meeting (2015)

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