Dearomatization and C-H deprotonation with heavier group 2 alkyls: does size matter?

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Abstract

We report that reaction of group 2 dialkyl compounds, [M{CH(SiMe3)(2)}(2)(THF)n] [M = Mg, Ca, n = 2; M = Sr, Ba, n = 3] with a bis(imino)pyridine ligand ultimately results in deprotonation of both methyl groups attached to the imine carbon center. The resulting compounds are mononuclear for M = Mg or Ca, but assemble into cyclic hexameric arrays when M = Sr or Ba. In all four cases deprotonation appears to occur by a common pathway involving pyridine dearomatization and subsequent deprotonation of a single imine-bound methyl substituent. Monitoring of each reaction has revealed that the efficacy of the transformation, as well as the stability of each intermediate, is dependent upon the identity, ionic radius, and resultant charge density of the alkaline earth reagent employed.
LanguageEnglish
Pages4203-4206
Number of pages4
JournalOrganometallics
Volume29
Issue number19
DOIs
StatusPublished - 11 Oct 2010

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Deprotonation
imines
pyridines
Imines
reagents
methylidyne
Charge density
ligands
radii
carbon
Carbon
Earth (planet)
Ligands
Monitoring
pyridine

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Dearomatization and C-H deprotonation with heavier group 2 alkyls: does size matter? / Arrowsmith, Merle; Hill, Michael S; Kociok-Kohn, Gabriele.

In: Organometallics, Vol. 29, No. 19, 11.10.2010, p. 4203-4206.

Research output: Contribution to journalArticle

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abstract = "We report that reaction of group 2 dialkyl compounds, [M{CH(SiMe3)(2)}(2)(THF)n] [M = Mg, Ca, n = 2; M = Sr, Ba, n = 3] with a bis(imino)pyridine ligand ultimately results in deprotonation of both methyl groups attached to the imine carbon center. The resulting compounds are mononuclear for M = Mg or Ca, but assemble into cyclic hexameric arrays when M = Sr or Ba. In all four cases deprotonation appears to occur by a common pathway involving pyridine dearomatization and subsequent deprotonation of a single imine-bound methyl substituent. Monitoring of each reaction has revealed that the efficacy of the transformation, as well as the stability of each intermediate, is dependent upon the identity, ionic radius, and resultant charge density of the alkaline earth reagent employed.",
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AB - We report that reaction of group 2 dialkyl compounds, [M{CH(SiMe3)(2)}(2)(THF)n] [M = Mg, Ca, n = 2; M = Sr, Ba, n = 3] with a bis(imino)pyridine ligand ultimately results in deprotonation of both methyl groups attached to the imine carbon center. The resulting compounds are mononuclear for M = Mg or Ca, but assemble into cyclic hexameric arrays when M = Sr or Ba. In all four cases deprotonation appears to occur by a common pathway involving pyridine dearomatization and subsequent deprotonation of a single imine-bound methyl substituent. Monitoring of each reaction has revealed that the efficacy of the transformation, as well as the stability of each intermediate, is dependent upon the identity, ionic radius, and resultant charge density of the alkaline earth reagent employed.

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