New supramolecular assemblies in heterobimetallic chemistry: synthesis of a homologous series of unsolvated alkali-metal zincates

David R. Armstrong, Helena S. Emerson, Alberto Hernán-Gómez, Alan R. Kennedy, Eva Hevia

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Using an interlocking co-complexation approach, a homologous series of unsolvated alkali-metal zincates [MZn(CH2SiMe3)3] (M = Li 1, Na 2, K 3) was prepared by reacting equimolar amounts of Zn(CH2SiMe3)2with the relevant alkali-metal alkyl M(CH2SiMe3) employing non-coordinating hexane as a solvent. X-ray crystallographic studies reveal that these heterobimetallic compounds exhibit unprecedented supramolecular assemblies made up exclusively of a three-fold combination of M-CH2, Zn-CH2and M⋯Me interactions. Revealing an important alkali-metal effect, 1 displays a linear chain structure; whereas 2 and 3 form much more intricate 3D and 2D coordination networks respectively. Shedding new light into the formation of these solvent-free zincates, DFT calculations indicate that the infinite degree of aggregation observed in 1-3 plays a major role in thermodynamically driving the co-complexation reactions of their homometallic precursors. NMR spectroscopic studies suggest that in C6D6solution 1-3 exist as discrete contacted ion-pair species, where the alkali-metal is partially solvated by molecules of deuterated solvent. The supramolecular assemblies of 1-3 can be easily deaggregated by adding the polydentate N-donors PMDETA (N,N,N′,N′′,N′′-pentamethyldiethylenetriamine) or TMEDA (N,N,N′,N′-tetramethylethylenediamine), affording monomeric [(PMDETA)LiZn(CH2SiMe3)3] (4) and [(TMEDA)2NaZn(CH2SiMe3)3] (5).

LanguageEnglish
Pages14229-14238
Number of pages10
JournalDalton Transactions
Volume43
Issue number38
Early online date15 May 2014
DOIs
Publication statusPublished - 14 Oct 2014

Fingerprint

Alkali Metals
Complexation
Hexanes
Discrete Fourier transforms
Agglomeration
Display devices
Nuclear magnetic resonance
Ions
X rays
Molecules
N,N,N',N'-tetramethylethylenediamine
phenyllithium

Keywords

  • heterobimetallic chemistry
  • unsolvated alkali-metal zincates
  • X-ray crystallographic study

Cite this

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abstract = "Using an interlocking co-complexation approach, a homologous series of unsolvated alkali-metal zincates [MZn(CH2SiMe3)3] (M = Li 1, Na 2, K 3) was prepared by reacting equimolar amounts of Zn(CH2SiMe3)2with the relevant alkali-metal alkyl M(CH2SiMe3) employing non-coordinating hexane as a solvent. X-ray crystallographic studies reveal that these heterobimetallic compounds exhibit unprecedented supramolecular assemblies made up exclusively of a three-fold combination of M-CH2, Zn-CH2and M⋯Me interactions. Revealing an important alkali-metal effect, 1 displays a linear chain structure; whereas 2 and 3 form much more intricate 3D and 2D coordination networks respectively. Shedding new light into the formation of these solvent-free zincates, DFT calculations indicate that the infinite degree of aggregation observed in 1-3 plays a major role in thermodynamically driving the co-complexation reactions of their homometallic precursors. NMR spectroscopic studies suggest that in C6D6solution 1-3 exist as discrete contacted ion-pair species, where the alkali-metal is partially solvated by molecules of deuterated solvent. The supramolecular assemblies of 1-3 can be easily deaggregated by adding the polydentate N-donors PMDETA (N,N,N′,N′′,N′′-pentamethyldiethylenetriamine) or TMEDA (N,N,N′,N′-tetramethylethylenediamine), affording monomeric [(PMDETA)LiZn(CH2SiMe3)3] (4) and [(TMEDA)2NaZn(CH2SiMe3)3] (5).",
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New supramolecular assemblies in heterobimetallic chemistry : synthesis of a homologous series of unsolvated alkali-metal zincates. / Armstrong, David R.; Emerson, Helena S.; Hernán-Gómez, Alberto; Kennedy, Alan R.; Hevia, Eva.

In: Dalton Transactions, Vol. 43, No. 38, 14.10.2014, p. 14229-14238.

Research output: Contribution to journalArticle

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AU - Emerson, Helena S.

AU - Hernán-Gómez, Alberto

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