Arene binding by silazido heavier alkaline earth cations
Related Experiment Video
Updated: Nov 3, 2026

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of Chalcogenidoplumbates(II or IV)
Published on: December 29, 2016
Oliver Jarvis1, Jacob T Guntley1, Michael S Hill1
1Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, UK. msh27@bath.ac.uk.
Abstract:
Reactions of [Ph3C]+[Al{OC(CF3)3}4]- with [Ae{N(SiMe3)2}2]2 (Ae = Ca, Sr) or [Ba{N(SiMe3)2}2(THF)]2 have been studied in benzene, mesitylene and chlorobenzene. Irrespective of Ae identity, interrogation of the bulk constitutions of the resultant systems was complicated by liquid clathrate formation. X-ray diffraction analysis of single crystals, however, identified the formation of bimetallic dications, [(η6-C6H6)Ae-μ-N(SiMe3)2]22+, and monometallic monocations, [(η6-1,3,5-Me3C6H3)2Ae-κ1-N(SiMe3)2]+ from benzene and mesitylene, respectively. In contrast, only the strontium system provided any indication of similar binding of chlorobenzene. Although these observations infer a greater binding affinity for the more electron rich arene derivative, in no case could any significant perturbation of the arene structure be identified. DFT calculations on the isolated cationic structures are consistent with this viewpoint, confirming the energetic similarity of both structural types and describing a decreasing affinity for arene binding in the order Ca > Sr > Ba. These calculations also invoke a notable level of nd-orbital participation in arene binding by [(Me3Si)2NAe(η6-arene)]+, which is all but negated by the adoption of an alternative silazide-bridged structure.
Related Concept Videos
Metal-Ligand Bonds
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
Complexation Equilibria: Factors Influencing Stability of Complexes
Complexation Equilibria: The Chelate Effect
Ionic Bonding and Electron Transfer
Formation of Complex Ions
Structural Isomerism
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can be...

