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Solvent‐Free and TMEDA‐Solvated Mixed Alkali Metal‐Magnesium Tris‐diisopropylamides
Author(s) -
Hevia Eva,
Kenley Fiona R.,
Kennedy Alan R.,
Mulvey Robert E.,
Rowlings René B.
Publication year - 2003
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200300413
Subject(s) - chemistry , isostructural , alkali metal , amide , magnesium , metal , solvent , tris , alkyl , inorganic chemistry , medicinal chemistry , chelation , polymer chemistry , crystallography , organic chemistry , crystal structure , biochemistry
A trio of heterobimetallic tris‐diisopropylamides, the solvent‐free potassium‐magnesium amide [{KMg(N i Pr 2 ) 3 } ∞ ], its TMEDA solvate [KMg(N i Pr 2 ) 3 ·TMEDA] and the sodium congener [NaMg(N i Pr 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‐(μ‐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. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)