Arene binding by silazido heavier alkaline earth cations.
- 1Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, UK. [email protected].
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.
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BibTeX
@article{jarvis2026arene,
title = {{Arene binding by silazido heavier alkaline earth cations.}},
author = {Oliver Jarvis and Jacob T Guntley and Michael S Hill and Mary F Mahon and Kyle G Pearce and Claire L McMullin},
journal = {Dalton transactions (Cambridge, England : 2003)},
year = {2026},
month = oct,
doi = {10.1039/d6dt02345b},
url = {https://europepmc.org/article/MED/42969339},
note = {CC BY},
}
RIS
TY - JOUR
TI - Arene binding by silazido heavier alkaline earth cations.
AU - Oliver Jarvis
AU - Jacob T Guntley
AU - Michael S Hill
AU - Mary F Mahon
AU - Kyle G Pearce
AU - Claire L McMullin
PY - 2026
DA - 2026/10/29
JO - Dalton transactions (Cambridge, England : 2003)
DO - 10.1039/d6dt02345b
UR - https://europepmc.org/article/MED/42969339
AB - 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.
SN - 1477-9226
SN - 1477-9234
ER -