Comparisons and contrasts in a complete set of alkali metal cumyl structures

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Ferguson, Paul D. L. and Anderson, David E. and Hevia, Eva and Horsley Downie, Thomas M. and Kennedy, Alan R. and Robertson, Stuart D. and Weetman, Catherine E. and Mulvey, Robert E. (2026) Comparisons and contrasts in a complete set of alkali metal cumyl structures. Inorganic Chemistry, 65 (14). 7993–8004. ISSN 1520-510X (https://doi.org/10.1021/acs.inorgchem.6c00468)

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Abstract

Alkali-metal benzyl complexes derived from toluene are known to vary their metal–ligand coordination mode as a function of the alkali-metal, with the metal transitioning from a typical σ bond to the anionic CH2 for lithium toward an interaction with the delocalized pi system of the aromatic ring as the metal gets larger and softer. Here, by switching to cumene, we report the charge-localizing effect of replacing the hydrogen atoms at the formally carbanionic carbon CH2 with electron-donating methyl groups in C(Me)2. NMR spectroscopic studies reveal competitive ring-metalation occurs, at the meta and para positions, alongside α-metalation on using an alkyl lithium base, with the meta- and α-isomers crystallographically characterized as a solvated dimer and monomer, respectively. Using Lochmann-Schlosser type base pairs to access the heavier alkali-metal complexes unveils only α-metalation. The presence of the methyl groups limits the variation in metal–ligand bonding, their electron-donating properties forcing the delocalization of the negative charge into the ring resulting in M-Ph interactions and sp2 hybridization at the formally deprotonated α-carbon regardless of the metal used. Considerable variation in aggregation state is observed with monomeric (Na), polymeric (K, Cs) and tetrameric (Rb) motifs identified in the solid-state.

ORCID iDs

Ferguson, Paul D. L. ORCID logoORCID: https://orcid.org/0009-0002-8155-4752, Anderson, David E., Hevia, Eva, Horsley Downie, Thomas M. ORCID logoORCID: https://orcid.org/0000-0001-5027-450X, Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, Robertson, Stuart D. ORCID logoORCID: https://orcid.org/0000-0002-9330-8770, Weetman, Catherine E. ORCID logoORCID: https://orcid.org/0000-0001-5643-9256 and Mulvey, Robert E. ORCID logoORCID: https://orcid.org/0000-0002-1015-2564;
  • Item type:Article
    ID code:95842
    Dates:
    Date
    Event
    13 April 2026
    Published
    27 March 2026
    Published Online
    17 March 2026
    Accepted
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:23 Mar 2026 12:08
    Last modified:04 Jun 2026 07:40
    URI:https://strathprints.strath.ac.uk/id/eprint/95842
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