Alkali metal reduction of alkali metal cations

Kyle G. Pearce, Han-Ying Liu, Samuel E. Neale, Hattie M. Goff, Mary F. Mahon, Claire L. McMullin () and Michael S. Hill ()
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Kyle G. Pearce: University of Bath
Han-Ying Liu: University of Bath
Samuel E. Neale: University of Bath
Hattie M. Goff: University of Bath
Mary F. Mahon: University of Bath
Claire L. McMullin: University of Bath
Michael S. Hill: University of Bath

Nature Communications, 2023, vol. 14, issue 1, 1-5

Abstract: Abstract Counter to synthetic convention and expectation provided by the relevant standard reduction potentials, the chloroberyllate, [{SiNDipp}BeClLi]2 [{SiNDipp} = {CH2SiMe2N(Dipp)}2; Dipp = 2,6-i-Pr2C6H3)], reacts with the group 1 elements (M = Na, K, Rb, Cs) to provide the respective heavier alkali metal analogues, [{SiNDipp}BeClM]2, through selective reduction of the Li+ cation. Whereas only [{SiNDipp}BeClRb]2 is amenable to reduction by potassium to its nearest lighter congener, these species may also be sequentially interconverted by treatment of [{SiNDipp}BeClM]2 by the successively heavier group 1 metal. A theoretical analysis combining density functional theory (DFT) with elemental thermochemistry is used to rationalise these observations, where consideration of the relevant enthalpies of atomisation of each alkali metal in its bulk metallic form proved crucial in accounting for experimental observations.

Date: 2023
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DOI: 10.1038/s41467-023-43925-5

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