Lee Wei-Ying, Liang Lan-Chang
Department of Chemistry and Center for Nanoscience & Nanotechnology, National Sun Yat-sen University, Kaohsiung 80424, Taiwan.
Dalton Trans. 2005 Jun 7(11):1952-6. doi: 10.1039/b502873f. Epub 2005 Apr 29.
The palladium-catalyzed aryl amination of 1-bromo-2-fluorobenzene with N,N-dimethylethylenediamine quantitatively produces N-(dimethylaminoethyl)-2-fluoroaniline, which subsequently reacts with KPPh2 in 1,4-dioxane to afford N-(dimethylaminoethyl)-2-diphenylphosphinoaniline (H[PNN]). The reactions of trialkylaluminium with H[PNN] in toluene generate the corresponding aluminium dialkyl complexes [PNN]AlR2 (R = Me, Et, i-Bu). The solution NMR spectroscopic and X-ray crystallographic studies are indicative of a trigonal bipyramidal geometry for these aluminium complexes in which the amino nitrogen atom is trans to the phosphorus donor of the [PNN]- ligand. This study presents rare examples of structurally characterized, five-coordinate aluminium hydrocarbyl complexes supported by phosphine-derived ligands.
钯催化1-溴-2-氟苯与N,N-二甲基乙二胺进行芳基胺化反应，定量生成N-(二甲基氨基乙基)-2-氟苯胺，该产物随后在1,4-二氧六环中与KPPh₂反应，得到N-(二甲基氨基乙基)-2-二苯基膦基苯胺（H[PNN]）。三烷基铝与H[PNN]在甲苯中反应生成相应的二烷基铝配合物[PNN]AlR₂（R = 甲基、乙基、异丁基）。溶液核磁共振光谱和X射线晶体学研究表明，这些铝配合物具有三角双锥几何构型，其中氨基氮原子与[PNN]⁻配体的磷供体呈反式。本研究展示了由膦衍生配体支撑的、结构已表征的五配位铝烃基配合物的罕见实例。
