Synthesis and structural characterisation of mixed alkalimetal-magnesium mixed ligand alkyl-amido ate complexes

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Andrikopoulos, Prokopis C. and Armstrong, D.R. and Kennedy, A.R. and Mulvey, R.E. and O'Hara, C.T. and Rowlings, Rene and Weatherstone, Susan (2007) Synthesis and structural characterisation of mixed alkalimetal-magnesium mixed ligand alkyl-amido ate complexes. Inorganica Chimica Acta, 360 (4). pp. 1370-1375. ISSN 0020-1693 (https://doi.org/10.1016/j.ica.2006.05.026)

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Abstract

Using two different reaction methodologies, two alkali metal–magnesium alkyl bis(amide) complexes were synthesised. First the lithium magnesiate LiMg{μ-N(SiMe3)2}2(tBu) (1) was prepared by combining equimolar quantities of tBuLi and Mg{N(SiMe3)2}2 in hydrocarbon solvent. An X-ray crystallographic study revealed that the asymmetric unit of 1 has a dinuclear arrangement, based on a planar Li–N–Mg–N four-membered ring. As a result of the presence of intermolecular agostic interactions between the Li centre of one asymmetric unit and a methyl group which is resident on the terminal tert-butyl group of another, 1 is polymeric in the solid-state. Second the sodium magnesiate NaMg{μ-N(SiMe3)2}2(tBu) · (OEt2) (2) was prepared by reacting two molar equivalents of Na{N(SiMe3)2} with one molar equivalent of tBuMgCl in hydrocarbon/diethyl ether solution. X-ray crystallographic analysis revealed that the asymmetric unit of 2 consisted of a dinuclear molecular arrangement. As expected it is not polymeric due to the coordination of the Lewis basic ether. Stabilizing intramolecular agostic NaC bonds are observed (where C is a methyl group resident on a Si atom).

ORCID iDs

Andrikopoulos, Prokopis C., Armstrong, D.R., Kennedy, A.R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, Mulvey, R.E. ORCID logoORCID: https://orcid.org/0000-0002-1015-2564, O'Hara, C.T., Rowlings, Rene and Weatherstone, Susan;
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