Aluminum Complexes Incorporating Bidentate Amido Phosphine Ligands
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- 作者：Lan-Chang Liang ; Mei-Hui Huang ; and Chen-Hsiung Hung
- 刊名：Inorganic Chemistry
- 出版年：2004
- 出版时间：March 22, 2004
- 年：2004
- 卷：43
- 期：6
- 页码：2166 - 2174
- 全文大小：204K
- 年卷期：v.43,no.6(March 22, 2004)
- ISSN：1520-510X
文摘
A series of aluminum complexes supported by o-phenylene-derived amido phosphine ligands, N-(2-diphenylphosphinophenyl)-2,6-dimethylanilide ([Me-NP]-) and N-(2-diphenylphosphinophenyl)-2,6-diisopropylanilide ([iPr-NP]-),have been prepared. The reactions of trialkylaluminum with H[Me-NP] and H[iPr-NP], respectively, in refluxingtoluene produced the corresponding dialkyl complexes [Me-NP]AlR2 and [iPr-NP]AlR2 (R = Me, Et). Deprotonationof H[Me-NP] with n-BuLi in THF at -35 
C followed by addition of AlCl3 in toluene at -35 C afforded [Me-NP]AlCl2, which was subsequently reacted with 2 equiv of trimethylsilylmethyllithium in toluene to give [Me-NP]Al(CH2SiMe3)2. The aluminum complexes were all characterized by 1H, 13C, 31P, and 27Al NMR spectroscopy. The solid-state structures of monomeric, four-coordinate [Me-NP]AlEt2 and [iPr-NP]AlMe2 and five-coordinate [Me-NP]AlCl2(THF)were determined by X-ray crystallography. The 1H NMR studies of [Me-NP]AlEt2, [Me-NP]Al(CH2SiMe3)2, and[iPr-NP]AlEt2 indicate diastereotopic 
-hydrogen atoms in these molecules. Heteronuclear COSY and NOEexperiments suggest that the phosphorus donor in [Me-NP]Al(CH2SiMe3)2 and [iPr-NP]AlEt2 is coupled to only oneof the diastereotopic -hydrogen atoms that is virtually antiperiplanar with respect to the phosphorus atom.
C followed by addition of AlCl3 in toluene at -35 C afforded [Me-NP]AlCl2, which was subsequently reacted with 2 equiv of trimethylsilylmethyllithium in toluene to give [Me-NP]Al(CH2SiMe3)2. The aluminum complexes were all characterized by 1H, 13C, 31P, and 27Al NMR spectroscopy. The solid-state structures of monomeric, four-coordinate [Me-NP]AlEt2 and [iPr-NP]AlMe2 and five-coordinate [Me-NP]AlCl2(THF)were determined by X-ray crystallography. The 1H NMR studies of [Me-NP]AlEt2, [Me-NP]Al(CH2SiMe3)2, and[iPr-NP]AlEt2 indicate diastereotopic -hydrogen atoms in these molecules. Heteronuclear COSY and NOEexperiments suggest that the phosphorus donor in [Me-NP]Al(CH2SiMe3)2 and [iPr-NP]AlEt2 is coupled to only oneof the diastereotopic -hydrogen atoms that is virtually antiperiplanar with respect to the phosphorus atom.