Synthesis and structures of [(trimethylsilyl)methyl]sodium and -potassium with bi- and tridentate n-donor ligands

William Clegg, Benjamin Grant Conway, Alan R. Kennedy, Jan Klett, Robert E. Mulvey, Luca Russo

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

[(Trimethylsilyl) methyl] sodium [NaCH2SiMe3] (1) was prepared by a metathesis reaction of [(trimethylsilyl) methyl] lithium [LiCH2SiMe3] with sodium tert-butoxide in n-hexane. Polydentate donors such as N,N,N',N'-tetramethylethylenediamine (TMEDA) and N,N,N', N '', N ''-pentamethyldiethylenetriamine (PMDETA) form n-hexane-soluble complexes of 1 and the potassium congener [KCH2SiMe3] (2). The crystal structures of the polymers [(TMEDA) NaCH2SiMe3] (1a) and [(PMDETA) KCH2SiMe3] (2a) were determined as infinite helical chains exhibiting 3(1) or 3(2) screw-axis symmetry. Compound 2b was obtained as the donor-deficient heterocubane pseudotetramer [(TMEDA)(3)(KCH2SiMe3)(4)], with intermolecular interactions of the TMEDA-uncoordinated potassium atom with a peripheral methyl group of a neighbouring tetramer to form infinite chains. The relatively easy accessibility and stability should make these (trimethylsilyl) methyl compounds of sodium and potassium valuable starting points for further exploration of the chemistry of these common-utility heavier alkali metals.

LanguageEnglish
Pages721-726
Number of pages6
JournalEuropean Journal of Inorganic Chemistry
Volume2011
Issue number5
DOIs
Publication statusPublished - Feb 2011

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Potassium
Sodium
Ligands
Potassium Compounds
Sodium Compounds
Alkali Metals
Lithium
Heavy metals
Polymers
Crystal structure
Atoms
N,N,N',N'-tetramethylethylenediamine
n-hexane

Keywords

  • aggregation
  • carbanions
  • sodium
  • potassium
  • n-donor ligands
  • ray crystal-structures
  • alkali-metal alkyls
  • organometallic compounds
  • thermal-decomposition
  • mediated zincation
  • aryl derivatives
  • strong bases
  • complexes
  • calcium
  • benzyl

Cite this

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title = "Synthesis and structures of [(trimethylsilyl)methyl]sodium and -potassium with bi- and tridentate n-donor ligands",
abstract = "[(Trimethylsilyl) methyl] sodium [NaCH2SiMe3] (1) was prepared by a metathesis reaction of [(trimethylsilyl) methyl] lithium [LiCH2SiMe3] with sodium tert-butoxide in n-hexane. Polydentate donors such as N,N,N',N'-tetramethylethylenediamine (TMEDA) and N,N,N', N '', N ''-pentamethyldiethylenetriamine (PMDETA) form n-hexane-soluble complexes of 1 and the potassium congener [KCH2SiMe3] (2). The crystal structures of the polymers [(TMEDA) NaCH2SiMe3] (1a) and [(PMDETA) KCH2SiMe3] (2a) were determined as infinite helical chains exhibiting 3(1) or 3(2) screw-axis symmetry. Compound 2b was obtained as the donor-deficient heterocubane pseudotetramer [(TMEDA)(3)(KCH2SiMe3)(4)], with intermolecular interactions of the TMEDA-uncoordinated potassium atom with a peripheral methyl group of a neighbouring tetramer to form infinite chains. The relatively easy accessibility and stability should make these (trimethylsilyl) methyl compounds of sodium and potassium valuable starting points for further exploration of the chemistry of these common-utility heavier alkali metals.",
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author = "William Clegg and Conway, {Benjamin Grant} and Kennedy, {Alan R.} and Jan Klett and Mulvey, {Robert E.} and Luca Russo",
year = "2011",
month = "2",
doi = "10.1002/ejic.201000983",
language = "English",
volume = "2011",
pages = "721--726",
journal = "European Journal of Inorganic Chemistry",
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Synthesis and structures of [(trimethylsilyl)methyl]sodium and -potassium with bi- and tridentate n-donor ligands. / Clegg, William; Conway, Benjamin Grant; Kennedy, Alan R.; Klett, Jan; Mulvey, Robert E.; Russo, Luca.

In: European Journal of Inorganic Chemistry, Vol. 2011, No. 5, 02.2011, p. 721-726.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Synthesis and structures of [(trimethylsilyl)methyl]sodium and -potassium with bi- and tridentate n-donor ligands

AU - Clegg, William

AU - Conway, Benjamin Grant

AU - Kennedy, Alan R.

AU - Klett, Jan

AU - Mulvey, Robert E.

AU - Russo, Luca

PY - 2011/2

Y1 - 2011/2

N2 - [(Trimethylsilyl) methyl] sodium [NaCH2SiMe3] (1) was prepared by a metathesis reaction of [(trimethylsilyl) methyl] lithium [LiCH2SiMe3] with sodium tert-butoxide in n-hexane. Polydentate donors such as N,N,N',N'-tetramethylethylenediamine (TMEDA) and N,N,N', N '', N ''-pentamethyldiethylenetriamine (PMDETA) form n-hexane-soluble complexes of 1 and the potassium congener [KCH2SiMe3] (2). The crystal structures of the polymers [(TMEDA) NaCH2SiMe3] (1a) and [(PMDETA) KCH2SiMe3] (2a) were determined as infinite helical chains exhibiting 3(1) or 3(2) screw-axis symmetry. Compound 2b was obtained as the donor-deficient heterocubane pseudotetramer [(TMEDA)(3)(KCH2SiMe3)(4)], with intermolecular interactions of the TMEDA-uncoordinated potassium atom with a peripheral methyl group of a neighbouring tetramer to form infinite chains. The relatively easy accessibility and stability should make these (trimethylsilyl) methyl compounds of sodium and potassium valuable starting points for further exploration of the chemistry of these common-utility heavier alkali metals.

AB - [(Trimethylsilyl) methyl] sodium [NaCH2SiMe3] (1) was prepared by a metathesis reaction of [(trimethylsilyl) methyl] lithium [LiCH2SiMe3] with sodium tert-butoxide in n-hexane. Polydentate donors such as N,N,N',N'-tetramethylethylenediamine (TMEDA) and N,N,N', N '', N ''-pentamethyldiethylenetriamine (PMDETA) form n-hexane-soluble complexes of 1 and the potassium congener [KCH2SiMe3] (2). The crystal structures of the polymers [(TMEDA) NaCH2SiMe3] (1a) and [(PMDETA) KCH2SiMe3] (2a) were determined as infinite helical chains exhibiting 3(1) or 3(2) screw-axis symmetry. Compound 2b was obtained as the donor-deficient heterocubane pseudotetramer [(TMEDA)(3)(KCH2SiMe3)(4)], with intermolecular interactions of the TMEDA-uncoordinated potassium atom with a peripheral methyl group of a neighbouring tetramer to form infinite chains. The relatively easy accessibility and stability should make these (trimethylsilyl) methyl compounds of sodium and potassium valuable starting points for further exploration of the chemistry of these common-utility heavier alkali metals.

KW - aggregation

KW - carbanions

KW - sodium

KW - potassium

KW - n-donor ligands

KW - ray crystal-structures

KW - alkali-metal alkyls

KW - organometallic compounds

KW - thermal-decomposition

KW - mediated zincation

KW - aryl derivatives

KW - strong bases

KW - complexes

KW - calcium

KW - benzyl

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U2 - 10.1002/ejic.201000983

DO - 10.1002/ejic.201000983

M3 - Article

VL - 2011

SP - 721

EP - 726

JO - European Journal of Inorganic Chemistry

T2 - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

SN - 1434-1948

IS - 5

ER -