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

doi:10.1021/ic8012766

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

Agricultural & Biological Engineering

Research output: Contribution to journal › Article › peer-review

41 Scopus citations

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 language	English (US)
Pages (from-to)	1380-1384
Number of pages	5
Journal	Inorganic chemistry
Volume	48
Issue number	4
DOIs	https://doi.org/10.1021/ic8012766
State	Published - Feb 16 2009

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{01d7592da60045ca865a05f3f5e0d1fd,

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.",

author = "Johns, {Adam M.} and Chmely, {Stephen C.} and Hanusa, {Timothy P.}",

year = "2009",

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doi = "10.1021/ic8012766",

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volume = "48",

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journal = "Inorganic chemistry",

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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.

PY - 2009/2/16

Y1 - 2009/2/16

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

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