Synthesis and crystal structure of trimeric sodium 2,2,6,6- tetramethylpiperidide (NaTMP)

B. Gehrhus, P.H. Hitchcock, A.R. Kennedy, M.F. Lappert, R.E. Mulvey, P.J.A. Rodger

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

The title compound has been synthesised in powder form by two distinct methods: namely by sodiation of the parent amine 2,2,6,6-tetramethylpiperidine with n-butylsodium in a hydrocarbon solvent or by transmetallation from lithium 2,2,6,6-tetramethylpiperidide through the action of sodium t-butoxide in hexane solution. An alternative crystalline specimen suitable for X-ray crystallographic study was grown from a solution which additionally contained n,s-dibutylmagnesium. This study reveals a trimeric molecule of C3h symmetry, its salient feature being a strictly planar (NaN)3 ring. The sterically encumbered amide anions are separated by large N---Na---N bond angles of 143.76(6)°, the bonding in which is slightly asymmetrical (Na---N bond lengths: 2.307(2) and 2.362(2) î..). Discussion focuses on the contrast between the tetrameric ring arrangement of the lithium congener, which was reported several years ago.
LanguageEnglish
JournalJournal of Organometallic Chemistry
Volume587
Issue number1
DOIs
Publication statusPublished - 15 Sep 1999

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Lithium
lithium
Crystal structure
Sodium
sodium
congeners
crystal structure
rings
Bond length
Hexanes
synthesis
Hydrocarbons
Hexane
Amides
Powders
amides
Amines
Anions
amines
Negative ions

Keywords

  • sodiation
  • 2
  • 6
  • 6-tetramethylpiperidine
  • n-butylsodium
  • X-ray crystallographic study

Cite this

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title = "Synthesis and crystal structure of trimeric sodium 2,2,6,6- tetramethylpiperidide (NaTMP)",
abstract = "The title compound has been synthesised in powder form by two distinct methods: namely by sodiation of the parent amine 2,2,6,6-tetramethylpiperidine with n-butylsodium in a hydrocarbon solvent or by transmetallation from lithium 2,2,6,6-tetramethylpiperidide through the action of sodium t-butoxide in hexane solution. An alternative crystalline specimen suitable for X-ray crystallographic study was grown from a solution which additionally contained n,s-dibutylmagnesium. This study reveals a trimeric molecule of C3h symmetry, its salient feature being a strictly planar (NaN)3 ring. The sterically encumbered amide anions are separated by large N---Na---N bond angles of 143.76(6)°, the bonding in which is slightly asymmetrical (Na---N bond lengths: 2.307(2) and 2.362(2) {\^i}..). Discussion focuses on the contrast between the tetrameric ring arrangement of the lithium congener, which was reported several years ago.",
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author = "B. Gehrhus and P.H. Hitchcock and A.R. Kennedy and M.F. Lappert and R.E. Mulvey and P.J.A. Rodger",
year = "1999",
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journal = "Journal of Organometallic Chemistry",
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Synthesis and crystal structure of trimeric sodium 2,2,6,6- tetramethylpiperidide (NaTMP). / Gehrhus, B.; Hitchcock, P.H.; Kennedy, A.R.; Lappert, M.F.; Mulvey, R.E.; Rodger, P.J.A.

In: Journal of Organometallic Chemistry, Vol. 587, No. 1, 15.09.1999.

Research output: Contribution to journalArticle

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T1 - Synthesis and crystal structure of trimeric sodium 2,2,6,6- tetramethylpiperidide (NaTMP)

AU - Gehrhus, B.

AU - Hitchcock, P.H.

AU - Kennedy, A.R.

AU - Lappert, M.F.

AU - Mulvey, R.E.

AU - Rodger, P.J.A.

PY - 1999/9/15

Y1 - 1999/9/15

N2 - The title compound has been synthesised in powder form by two distinct methods: namely by sodiation of the parent amine 2,2,6,6-tetramethylpiperidine with n-butylsodium in a hydrocarbon solvent or by transmetallation from lithium 2,2,6,6-tetramethylpiperidide through the action of sodium t-butoxide in hexane solution. An alternative crystalline specimen suitable for X-ray crystallographic study was grown from a solution which additionally contained n,s-dibutylmagnesium. This study reveals a trimeric molecule of C3h symmetry, its salient feature being a strictly planar (NaN)3 ring. The sterically encumbered amide anions are separated by large N---Na---N bond angles of 143.76(6)°, the bonding in which is slightly asymmetrical (Na---N bond lengths: 2.307(2) and 2.362(2) î..). Discussion focuses on the contrast between the tetrameric ring arrangement of the lithium congener, which was reported several years ago.

AB - The title compound has been synthesised in powder form by two distinct methods: namely by sodiation of the parent amine 2,2,6,6-tetramethylpiperidine with n-butylsodium in a hydrocarbon solvent or by transmetallation from lithium 2,2,6,6-tetramethylpiperidide through the action of sodium t-butoxide in hexane solution. An alternative crystalline specimen suitable for X-ray crystallographic study was grown from a solution which additionally contained n,s-dibutylmagnesium. This study reveals a trimeric molecule of C3h symmetry, its salient feature being a strictly planar (NaN)3 ring. The sterically encumbered amide anions are separated by large N---Na---N bond angles of 143.76(6)°, the bonding in which is slightly asymmetrical (Na---N bond lengths: 2.307(2) and 2.362(2) î..). Discussion focuses on the contrast between the tetrameric ring arrangement of the lithium congener, which was reported several years ago.

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