Sadique A R, Heeg M J, Winter C H
Department of Chemistry, Wayne State University, Detroit, MI 48202, USA.
Inorg Chem. 2001 Dec 3;40(25):6349-55. doi: 10.1021/ic0106928.
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-ethylacetamidinato)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-ethylacetamidinato)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(N,N'-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 degrees C. 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.
在室温下，将无水溴化镁与2当量的（1,3 - 二叔丁基乙脒基）锂、（1,3 - 二叔丁基苯脒基）锂、（1,3 - 二异丙基乙脒基）锂或（1 - 叔丁基 - 3 - 乙基乙脒基）锂（由相应的碳二亚胺和烷基锂原位制备）在乙醚中反应，分别得到无色结晶固体双（N，N'-二叔丁基乙脒基）镁（81%）、双（N，N'-二叔丁基苯脒基）镁（82%）、双[双（N，N'-二异丙基乙脒基）镁]（70%）或双[双（1 - 叔丁基 - 3 - 乙基乙脒基）镁]（93%）。通过光谱和分析数据以及对双（N，N'-二叔丁基苯脒基）镁、双[双（N，N'-二异丙基乙脒基）镁]和双[双（1 - 叔丁基 - 3 - 乙基乙脒基）镁]进行单晶X射线晶体学分析对这些配合物进行了表征。在固态结构中，发现双[双（1 - 叔丁基 - 3 - 乙基乙脒基）镁]含有μ，η(2):η(1)-脒基配体。双[双（N，N'-二异丙基乙脒基）镁]在-20至+60℃之间的甲苯-d(8)中存在单体 - 二聚体平衡。对该平衡进行范特霍夫分析得到ΔH° = -14.7±0.2 kcal/mol，ΔS° = -44.9±0.2 cal/(mol·K)，以及ΔG°(298 K) = -1.32±0.2 kcal/mol。讨论了这些新化合物在镁掺杂的13族化合物半导体薄膜化学气相沉积中的潜在应用。
