By Halogen‐Lithium Exchange with Organic Halides
            <sup>1‐2</sup>

Wardell, Jámes L.

doi:10.1002/9780470145258.ch9

Cited by 5 publications

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The Role of Ate Complexes in Halogen(Metalloid)–Metal Exchange Reactions: A Theoretical Study

Boche¹,

Schimeczek

Ciosłowski³

et al. 1998

Eur. J. Org. Chem.

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Correlated electronic structure calculations predict that [(CH3)n+1X]− methyl ate anions, where X is an element of the main groups 14, 15, 16, or 17 up to Bi, possess widely varying stabilities that are governed by the electronegativities of their central atoms X. These stabilities correlate well with the propensities of the elements in question to undergo exchange with lithium and magnesium halide, except in the cases where steric hindrance in the transition states of the exchange reactions is important. These findings are nicely confirmed by calculations of the transition states [(CH3)2XLi]# (X = Cl, Br, I) and [(CH3)3SeLi]# of the corresponding degenerate exchange reactions CH3X (X = Cl, Br, I) + CH3Li and (CH3)2Se + CH3Li, respectively. The computed relative stabilities of the mixed [R–I–CH3]− ate anions of iodine (where R = phenyl, ethynyl, vinyl, ethyl, or cyclopropyl) are in excellent agreement with the experimentally observed equilibria of the corresponding lithium–iodine exchange reactions. The recent experimental observation of a highly stable α‐iodine‐substituted iodine ate complex as an intermediate in an iodine–magnesium bromide exchange reaction is also corroborated by our studies. Thus, the present calculations provide strong evidence for ate complexes being key intermediates in halogen(metalloid)–lithium(magnesium halide) exchange reactions.

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