Solution interaction of potassium and calcium bis(trimethylsilyl)amides; preparation of Ca[N(SiMe 3) 2] 2 from dibenzylcalcium

Adam M. Johns, Stephen C. Chmely, Timothy P. Hanusa

Research output: Contribution to journalArticle

34 Citations (Scopus)

Abstract

Ca[N(SiMe 3) 2] 2 (1) is isolated in nearly quantitative yield from the room temperature reaction of Ca(CH 2Ph) 2(THF) and HN(SiMe 3) 2 in toluene. A commonly used preparation of 1 involving the reaction of potassium bis(trimethylsilyl)amide, K[N(SiMe 3) 2] (2), with Cal 2 can produce material that contains substantial amounts of potassium, probably in the form of a calciate such as K[Ca{N(SiMe 3) 2} 3]. The favorable formation of K[Ca{N(SiMe 3) 2} 3] from 1 and 2 was confirmed with density functional theory calculations. Deliberate doping of solutions of 1 with 2 initially causes only an upfield shift in the single 1H NMR resonance observed for 1; not until K/Ca ratios exceed 1:1 is the presence of the added potassium obvious by the appearance of an additional peak in the spectrum.

Original languageEnglish (US)
Pages (from-to)1380-1384
Number of pages5
JournalInorganic chemistry
Volume48
Issue number4
DOIs
StatePublished - Feb 16 2009

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amides
calcium
potassium
Potassium
preparation
Toluene
interactions
Amides
Density functional theory
toluene
Doping (additives)
Nuclear magnetic resonance
methylidyne
density functional theory
nuclear magnetic resonance
causes
shift
room temperature
calcium bis(trimethylsilyl)amide
Temperature

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

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title = "Solution interaction of potassium and calcium bis(trimethylsilyl)amides; preparation of Ca[N(SiMe 3) 2] 2 from dibenzylcalcium",
abstract = "Ca[N(SiMe 3) 2] 2 (1) is isolated in nearly quantitative yield from the room temperature reaction of Ca(CH 2Ph) 2(THF) and HN(SiMe 3) 2 in toluene. A commonly used preparation of 1 involving the reaction of potassium bis(trimethylsilyl)amide, K[N(SiMe 3) 2] (2), with Cal 2 can produce material that contains substantial amounts of potassium, probably in the form of a calciate such as K[Ca{N(SiMe 3) 2} 3]. The favorable formation of K[Ca{N(SiMe 3) 2} 3] from 1 and 2 was confirmed with density functional theory calculations. Deliberate doping of solutions of 1 with 2 initially causes only an upfield shift in the single 1H NMR resonance observed for 1; not until K/Ca ratios exceed 1:1 is the presence of the added potassium obvious by the appearance of an additional peak in the spectrum.",
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Solution interaction of potassium and calcium bis(trimethylsilyl)amides; preparation of Ca[N(SiMe 3) 2] 2 from dibenzylcalcium. / Johns, Adam M.; Chmely, Stephen C.; Hanusa, Timothy P.

In: Inorganic chemistry, Vol. 48, No. 4, 16.02.2009, p. 1380-1384.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Solution interaction of potassium and calcium bis(trimethylsilyl)amides; preparation of Ca[N(SiMe 3) 2] 2 from dibenzylcalcium

AU - Johns, Adam M.

AU - Chmely, Stephen C.

AU - Hanusa, Timothy P.

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N2 - Ca[N(SiMe 3) 2] 2 (1) is isolated in nearly quantitative yield from the room temperature reaction of Ca(CH 2Ph) 2(THF) and HN(SiMe 3) 2 in toluene. A commonly used preparation of 1 involving the reaction of potassium bis(trimethylsilyl)amide, K[N(SiMe 3) 2] (2), with Cal 2 can produce material that contains substantial amounts of potassium, probably in the form of a calciate such as K[Ca{N(SiMe 3) 2} 3]. The favorable formation of K[Ca{N(SiMe 3) 2} 3] from 1 and 2 was confirmed with density functional theory calculations. Deliberate doping of solutions of 1 with 2 initially causes only an upfield shift in the single 1H NMR resonance observed for 1; not until K/Ca ratios exceed 1:1 is the presence of the added potassium obvious by the appearance of an additional peak in the spectrum.

AB - Ca[N(SiMe 3) 2] 2 (1) is isolated in nearly quantitative yield from the room temperature reaction of Ca(CH 2Ph) 2(THF) and HN(SiMe 3) 2 in toluene. A commonly used preparation of 1 involving the reaction of potassium bis(trimethylsilyl)amide, K[N(SiMe 3) 2] (2), with Cal 2 can produce material that contains substantial amounts of potassium, probably in the form of a calciate such as K[Ca{N(SiMe 3) 2} 3]. The favorable formation of K[Ca{N(SiMe 3) 2} 3] from 1 and 2 was confirmed with density functional theory calculations. Deliberate doping of solutions of 1 with 2 initially causes only an upfield shift in the single 1H NMR resonance observed for 1; not until K/Ca ratios exceed 1:1 is the presence of the added potassium obvious by the appearance of an additional peak in the spectrum.

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