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Updated: Jul 19, 2025

Synthesis of Nine-atom Deltahedral Zintl Ions of Germanium and their Functionalization with Organic Groups
Published on: February 11, 2012
Calix[4]pyrrolato-germane-(thf)2: Unlocking the Anti-van't Hoff-Le Bel Reactivity of Germanium(IV) by Ligand
Ravi Yadav1, Paul Janßen1, Marcel Schorpp1
1Anorganisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Heidelberg 69120, Germany.
Abstract:
Anti-van't Hoff-Le Bel configured p-block element species possess intrinsically high reactivity and are thus challenging to isolate. Consequently, numerous elements in this configuration, including square-planar germanium(IV), remain unexplored. Herein, we follow a concept to reach anti-van't Hoff-Le Bel reactivity by ligand dissociation from a rigid calix[4]pyrrole germane in its bis(thf) adduct. While the macrocyclic ligand assures square-planar coordination in the uncomplexed form, the labile thf donors provide robustness for isolation on a multigram scale. Unique properties of a low-lying acceptor orbital imparted to germanium(IV) can be verified, e.g., by isolating an elusive anionic hydrido germanate and exploiting it for challenging bond activations. Aldehydes, water, alcohol, and a CN triple bond are activated for the first time by germanium-ligand cooperativity. Unexpected behaviors against fluoride ion donors disclose critical interferences of a putative redox-coupled fluoride ion transfer during the experimental determination of Lewis acidity. Overall, we showcase how ligand lability grants access to the uncharted chemistry of anti-van't Hoff-Le Bel germanium(IV) and line up this element as a member in the emerging class of structurally constrained p-block elements.
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