Examination of Structure and Bonding in 10-Coordinate Europium and Americium Terpyridyl Complexes

Inorg Chem. 2018 Oct 15;57(20):12969-12975. doi: 10.1021/acs.inorgchem.8b02085. Epub 2018 Sep 28.

Abstract

M(TpyNO2)(NO3)3(H2O)·THF (M = La, Nd, Sm, Eu, Tb, Am; TpyNO2 = 4'-nitrophenyl terpyridyl) have been prepared from the reaction of M(NO3)3· nH2O with TpyNO2 in THF. Structural analysis shows that the metal centers are 10-coordinate, providing the first example of AmIII with this coordination number. Further spectroscopic and theoretical evaluation of these complexes reveals utilization of the 5f orbitals in bonding in the AmIII complex. Comparison of Nd-L, Eu-L, and Am-L bond distances demonstrates that some caution should be taken in comparing EuIII versus AmIII in extraction experiments.