Gross rearrangement of Fe(II) aggregate structure by replacement of two H+ by two Li+: Visualizing altered structure of acid versus conjugate base

摘要

Double deprotonation of [(H2L)FeCl2](2)center dot FeCl2 with LiN(SiMe3)(2) under varying conditions occurs to give the acid [(THF)(2)LiClFe2L2](2)[Fe(OH)(2)], 1, and the lithium salt of its doubly deprotonated conjugate base Li-2([(THF)(1.5)LiClFe2L2](2)[Fe(O)(2)]), 2. Single crystal X-ray determination of both structures shows that replacement of two protons by two Li+ causes both oxo and chloride ligands to adopt higher connectivity bridging roles. This illustrates the core event of moving towards more closed and higher dimensionality. The added lithium ions bind to various nucleophilic centers in the resulting intimate ion pair, all with general contraction of the metal framework, as an illustration of the general shrinkage towards a compact solid as hydroxide is converted to oxide. (C) 2019 Published by Elsevier Ltd.