Solid state and solution studies of lithium tris(n-butyl)magnesiates stabilised by Lewis donors

Zaragoza-Calero, Silvia and Francos, Javier and Kennedy, Alan R. and O'Hara, Charles T. (2015) Solid state and solution studies of lithium tris(n-butyl)magnesiates stabilised by Lewis donors. Dalton Transactions, 44 (16). pp. 7258-7267. ISSN 1477-9234 (

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Several Lewis base adducts of the synthetically important lithium tris(n-butyl)magnesiate LiMg(nBu)3 have been prepared and structurally characterised. The complexes were prepared by a co-complexation approach i.e., by combining the monometallic nBuLi and nBu2Mg reagents in hydrocarbon solution before adding a molar equivalent of a donor molecule (a bidentate amine, tridentate amine or cyclic ether). The lithium magnesiates all adopt variants of the "Weiss motif" structure, i.e., contacted ion pair dimers with a linear arrangement and metals connected by butyl anions, where tetrahedral magnesium ions are in the central positions and the lithiums occupy the outer region, solvated by a neutral Lewis donor [(donor)Li([small mu ]-nBu)2Mg([small mu ]-nBu)2Mg([small mu ]-nBu)2Li(donor)]. When TMPDA, PMDETA or (R,R)-TMCDA [TMPDA = N,N,N[prime or minute]N[prime or minute]-tetramethylpropanediamine; PMDETA = N,N,N[prime or minute],N[prime or minute][prime or minute],N[prime or minute][prime or minute]-pentamethyldiethylenetriamine; and (R,R)-TMCDA = (R,R)-N,N,N[prime or minute],N[prime or minute]-tetramethylcyclohexane-1,2-diamine], are employed, dimeric tetranuclear lithium magnesiates are produced. Due to the tridentate nature of the ligand, the PMDETA-containing structure (2) has an unusual 'open'-motif. When TMEDA (TMEDA = N,N,N[prime or minute],N[prime or minute]-tetramethylethylenediamine) is employed, a n-butoxide-containing complex [(TMEDA)Li([small mu ]-nBu)([small mu ]-OnBu)Mg2(nBu)2([small mu ]-nBu)([small mu ]-OnBu)Li(donor)] has been serendipitously prepared and adopts a ladder conformation which is commonly observed in lithium amide chemistry. This complex has also been prepared using a rational methodology. When 1,4-dioxane is employed, the donor stitches together a polymeric array of tetranuclear dimeric units (6). The hydrocarbon solution structures of the compounds have been characterised by 1H, 7Li, 13C NMR spectroscopy; 2 has been studied by variable temperature and DOSY NMR.


Zaragoza-Calero, Silvia, Francos, Javier, Kennedy, Alan R. ORCID logoORCID: and O'Hara, Charles T.;