Monomeric and dimeric amidinate complexes of magnesium

Treatment of anhydrous magnesium bromide with 2 equiv of (1,3-di-tert-butylacetamidinato)lithium, (1,3-di-tert-butylbenzamidinato)lithium, (1,3-diisopropylacetamidinato)lithium, or (1-tert-butyl-3-ethylacetaniidinato)lithium (prepared in situ from the corresponding carbodiimide and alkyllithium) in diethyl ether at ambient temperature afforded bis(N,N'-di-tert-butylacetamidinato)magnesium (81%), bis(N,N'-di-tert-butylbenzamidinato)magnesium (82%), bis[bis(N,N'-diisopropylacetamidinato)magnesium] (70%), or bis[bis(1-tert-butyl-3-ethyl-acetamidinato)magnesium] (93%) respectively, as colorless crystalline solids. These complexes were characterized by spectral and analytical data and by single-crystal X-ray crystallography for bis(NAr-di-tert-butylbenzamidinato)magnesium, bis[bis(N,N'-diisopropylacetamidinato)magnesium], and bis[bis(1-tert-butyl-3-ethylacetamidinato)magnesium]. In the solid-state structure, bis[bis(1-tert-butyl-3-ethylacetamidinato)magnesium] was found to contain mu,eta (2):eta (1)-amidinato ligands. Bis[bis(N,N'-diisopropylacetamidinato)magnesium] exists in a monomer-dimer equilibrium in toluene-d(8) between -20 and +60 degreesC. A van't Hoff analysis of this equilibrium afforded DeltaH degrees = - 14.7 +/- 0.2 kcal/mol, DeltaS degrees = -44.9 +/- 0.2 cal/(mol(.)K), and DeltaG degrees (298 K) = -1.32 +/- 0.2 kcal/mol. The potential application of the new compounds in the chemical vapor deposition of magnesium-doped group 13 compound semiconductor films is discussed.