Synthesis and structural elucidation of a rare example of a tris(amido) potassium magnesiate

Ben J. Fleming, Pablo Garcia-Alvarez, Elizabeth Keating, Alan Kennedy, Charles O'Hara

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

An equimolar quantity of benzylpotassium and di-n-butylmagnesium were combined with three molar equivalents of diphenylamine in a solvent medium which consisted on THF, hexane and N,N,N',N',N ''-pentamethyldiethylenetriamine (PMDETA). This mixture produces a rare example of a potassium tris(amido) magnesiate, namely (PMDETA)center dot K(mu-NPh2)Mg(THF)(NPh2)(2) 1. Complex 1 was characterized by X-ray crystallography and H-1 and C-13 NMR spectroscopy. The solid state structure of 1 (particularly the metals' co-ordination spheres) differs considerably from that of previously characterized potassium magnesiates, presumably due to the less sterically demanding nature of the amido ligand employed in this study. The magnesium center is four-coordinate (usually three-coordinate in such ate systems) and as well as binding to three amido ligands, is coordinated to a THF molecule. Turning to the potassium center, it is bound to three N centers from the triamine PMDETA, only one amido group, and its coordination sphere is completed by a series of aryl-pi contacts. The H-1 NMR solution studies in C6D6 appear to show that the complex does not stay intact in arene but likely forms a solvent-separated species such as [K(C6D6)(x)](+)[(THF) Mg(NPh2)(3)]. 

LanguageEnglish
Pages154-157
Number of pages4
JournalInorganica Chimica Acta
Volume384
DOIs
Publication statusPublished - 1 Apr 2012

Fingerprint

Potassium
potassium
synthesis
Ligands
Diphenylamine
X ray crystallography
Hexanes
Hexane
Contacts (fluid mechanics)
Magnesium
nuclear magnetic resonance
ligands
Nuclear magnetic resonance spectroscopy
guy wires
Metals
Nuclear magnetic resonance
crystallography
magnesium
Molecules
solid state

Keywords

  • structural elucidation
  • tris(amido) potassium magnesiate
  • spectroscopy

Cite this

Fleming, Ben J. ; Garcia-Alvarez, Pablo ; Keating, Elizabeth ; Kennedy, Alan ; O'Hara, Charles. / Synthesis and structural elucidation of a rare example of a tris(amido) potassium magnesiate. In: Inorganica Chimica Acta. 2012 ; Vol. 384. pp. 154-157.
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Synthesis and structural elucidation of a rare example of a tris(amido) potassium magnesiate. / Fleming, Ben J.; Garcia-Alvarez, Pablo; Keating, Elizabeth; Kennedy, Alan; O'Hara, Charles.

In: Inorganica Chimica Acta, Vol. 384, 01.04.2012, p. 154-157.

Research output: Contribution to journalArticle

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AB - An equimolar quantity of benzylpotassium and di-n-butylmagnesium were combined with three molar equivalents of diphenylamine in a solvent medium which consisted on THF, hexane and N,N,N',N',N ''-pentamethyldiethylenetriamine (PMDETA). This mixture produces a rare example of a potassium tris(amido) magnesiate, namely (PMDETA)center dot K(mu-NPh2)Mg(THF)(NPh2)(2) 1. Complex 1 was characterized by X-ray crystallography and H-1 and C-13 NMR spectroscopy. The solid state structure of 1 (particularly the metals' co-ordination spheres) differs considerably from that of previously characterized potassium magnesiates, presumably due to the less sterically demanding nature of the amido ligand employed in this study. The magnesium center is four-coordinate (usually three-coordinate in such ate systems) and as well as binding to three amido ligands, is coordinated to a THF molecule. Turning to the potassium center, it is bound to three N centers from the triamine PMDETA, only one amido group, and its coordination sphere is completed by a series of aryl-pi contacts. The H-1 NMR solution studies in C6D6 appear to show that the complex does not stay intact in arene but likely forms a solvent-separated species such as [K(C6D6)(x)](+)[(THF) Mg(NPh2)(3)]. 

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