Solvent-free and TMEDA-solvated mixed alkali metal-magnesium tris-diisopropylamides

E. Hevia, F.R. Kenley, A.R. Kennedy, R.E. Mulvey, R.B. Rowlings

Research output: Contribution to journalArticle

30 Citations (Scopus)

Abstract

A trio of heterobimetallic tris-diisopropylamides, the solvent-free potassium-magnesium amide [{KMg(NiPr2)(3)}(infinity)], its TMEDA solvate [KMg(NiPr2)(3).TMEDA] and the sodium congener [NaMg(NjPr(2))(3).TMEDA] has been synthesised by mixing the appropriate metal alkyl reagents with three molar equivalents of diisopropylamine in a hydrocarbon medium, to which, in the last two cases, TMEDA is added. All three amides have been successfully crystallographically characterised by X-ray diffraction studies. Representing the first pure s-block mixed-metal diisopropylamide free of solvent molecules or other stabilising anionic co-ligands, the first compound adopts an infinite spiral chain of ...K-(mu-N)(2)-Mg-N... links, the metal-N framework of which is supported by agostic K...C intra-dinuclear and inter-dinuclear contacts. The dinuclear tris-amido motif is maintained in both TMEDA complexes, the metal-N cores of which are essentially isostructural, but the presence of the chelating diamine blocks the propagating terminal site on the alkali metal and so gives rise to discrete molecular structures.
LanguageEnglish
Pages3347-3353
Number of pages6
JournalEuropean Journal of Inorganic Chemistry
Volume2003
Issue number18
DOIs
Publication statusPublished - 26 Sep 2003

Fingerprint

Alkali Metals
Magnesium
Metals
Amides
Diamines
Hydrocarbons
Chelation
Molecular structure
Potassium
Sodium
Ligands
X ray diffraction
Molecules
phenyllithium

Keywords

  • alkali metals
  • N ligands
  • heterometallic complexes
  • potassium
  • magnesium

Cite this

@article{5b37755c59c34d46bacc2a022ec82a05,
title = "Solvent-free and TMEDA-solvated mixed alkali metal-magnesium tris-diisopropylamides",
abstract = "A trio of heterobimetallic tris-diisopropylamides, the solvent-free potassium-magnesium amide [{KMg(NiPr2)(3)}(infinity)], its TMEDA solvate [KMg(NiPr2)(3).TMEDA] and the sodium congener [NaMg(NjPr(2))(3).TMEDA] has been synthesised by mixing the appropriate metal alkyl reagents with three molar equivalents of diisopropylamine in a hydrocarbon medium, to which, in the last two cases, TMEDA is added. All three amides have been successfully crystallographically characterised by X-ray diffraction studies. Representing the first pure s-block mixed-metal diisopropylamide free of solvent molecules or other stabilising anionic co-ligands, the first compound adopts an infinite spiral chain of ...K-(mu-N)(2)-Mg-N... links, the metal-N framework of which is supported by agostic K...C intra-dinuclear and inter-dinuclear contacts. The dinuclear tris-amido motif is maintained in both TMEDA complexes, the metal-N cores of which are essentially isostructural, but the presence of the chelating diamine blocks the propagating terminal site on the alkali metal and so gives rise to discrete molecular structures.",
keywords = "alkali metals, N ligands, heterometallic complexes, potassium, magnesium",
author = "E. Hevia and F.R. Kenley and A.R. Kennedy and R.E. Mulvey and R.B. Rowlings",
year = "2003",
month = "9",
day = "26",
doi = "10.1002/ejic.200300413",
language = "English",
volume = "2003",
pages = "3347--3353",
journal = "European Journal of Inorganic Chemistry",
issn = "1434-1948",
number = "18",

}

Solvent-free and TMEDA-solvated mixed alkali metal-magnesium tris-diisopropylamides. / Hevia, E.; Kenley, F.R.; Kennedy, A.R.; Mulvey, R.E.; Rowlings, R.B.

In: European Journal of Inorganic Chemistry, Vol. 2003, No. 18, 26.09.2003, p. 3347-3353.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Solvent-free and TMEDA-solvated mixed alkali metal-magnesium tris-diisopropylamides

AU - Hevia, E.

AU - Kenley, F.R.

AU - Kennedy, A.R.

AU - Mulvey, R.E.

AU - Rowlings, R.B.

PY - 2003/9/26

Y1 - 2003/9/26

N2 - A trio of heterobimetallic tris-diisopropylamides, the solvent-free potassium-magnesium amide [{KMg(NiPr2)(3)}(infinity)], its TMEDA solvate [KMg(NiPr2)(3).TMEDA] and the sodium congener [NaMg(NjPr(2))(3).TMEDA] has been synthesised by mixing the appropriate metal alkyl reagents with three molar equivalents of diisopropylamine in a hydrocarbon medium, to which, in the last two cases, TMEDA is added. All three amides have been successfully crystallographically characterised by X-ray diffraction studies. Representing the first pure s-block mixed-metal diisopropylamide free of solvent molecules or other stabilising anionic co-ligands, the first compound adopts an infinite spiral chain of ...K-(mu-N)(2)-Mg-N... links, the metal-N framework of which is supported by agostic K...C intra-dinuclear and inter-dinuclear contacts. The dinuclear tris-amido motif is maintained in both TMEDA complexes, the metal-N cores of which are essentially isostructural, but the presence of the chelating diamine blocks the propagating terminal site on the alkali metal and so gives rise to discrete molecular structures.

AB - A trio of heterobimetallic tris-diisopropylamides, the solvent-free potassium-magnesium amide [{KMg(NiPr2)(3)}(infinity)], its TMEDA solvate [KMg(NiPr2)(3).TMEDA] and the sodium congener [NaMg(NjPr(2))(3).TMEDA] has been synthesised by mixing the appropriate metal alkyl reagents with three molar equivalents of diisopropylamine in a hydrocarbon medium, to which, in the last two cases, TMEDA is added. All three amides have been successfully crystallographically characterised by X-ray diffraction studies. Representing the first pure s-block mixed-metal diisopropylamide free of solvent molecules or other stabilising anionic co-ligands, the first compound adopts an infinite spiral chain of ...K-(mu-N)(2)-Mg-N... links, the metal-N framework of which is supported by agostic K...C intra-dinuclear and inter-dinuclear contacts. The dinuclear tris-amido motif is maintained in both TMEDA complexes, the metal-N cores of which are essentially isostructural, but the presence of the chelating diamine blocks the propagating terminal site on the alkali metal and so gives rise to discrete molecular structures.

KW - alkali metals

KW - N ligands

KW - heterometallic complexes

KW - potassium

KW - magnesium

UR - http://dx.doi.org/10.1002/ejic.200300413

U2 - 10.1002/ejic.200300413

DO - 10.1002/ejic.200300413

M3 - Article

VL - 2003

SP - 3347

EP - 3353

JO - European Journal of Inorganic Chemistry

T2 - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

SN - 1434-1948

IS - 18

ER -