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首页> 外文期刊>Organometallics >Synthesis and structural characterization of neutral and cationic alkylaluminum complexes based on bidentate aminophenolate ligands
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Synthesis and structural characterization of neutral and cationic alkylaluminum complexes based on bidentate aminophenolate ligands

机译：基于二齿氨基酚酸酯配体的中性和阳离子烷基铝配合物的合成和结构表征

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The reaction of the aminophenols 2-(CH2L)-6-R-C6H3OH (R = Ph, L = NMe2, 1a; R = Bu-t, L = NMe2, 1b; R = Bu-t, L = NC4H8, 1c; R = Bu-t, L = NC5H10, 1d) with 1 equiv of AlMe3 affords the corresponding dimethyl Al complexes {2-(CH2L)-6-R-C6H3O}AlMe2 (R = Ph, L = NMe2, 2a; R = Bu-t, L = NMe2, 2b; R = Bu-t, L = NC4H8, 2c; R = Bu-t, L = NC5H10, 2d) in high yields. Compounds 2a-d appear to be monomeric, on the basis of X-ray analysis for 2b,d and NMR data for 2a-d, and are stable in the presence of THF. {2-(CH2NMe2)-6-Ph-C6H3O}AlMe2 (2a) cleanly reacts with B(C6F5)(3) to yield the dinuclear cationic Al species 3a(+). X-ray diffraction analysis shows that the cation 3a(+) can be seen as an adduct of the three-coordinate cation {2-(CH2NMe2)-6-Ph-C6H3O}AlMe+ and the neutral precursor 2a, in which the two Al centers are connected via a mu(2)-O aminophenolate bridge. Similarly, the reaction of Al dimethyl complexes 2b-d with B(C6F5)(3) yields dinuclear cationic Al species 3b-d(+)/3b'-d'+ (3b+/3b'(+) in a 1/1 ratio; 3c,d+/3c',d'(+) in a 3/1 ratio, respectively) as diastereomeric mixtures. Cations 3b-d(+)/3b'-d'(+) adopt a structure similar to that of cation 3a(+), as determined by X-ray crystallography analysis for 3b'(+) and 2D NMR studies for 3a(+) and 3c,d+/3c',d'+. All the formed dinuclear cations are quite stable and robust in solution, and no fluxional behavior for any of them was observed up to 80 degreesC in C6D5Br. Cations 3b-d(+)/3b'-d'(+) react with a Lewis base such as THF to afford the corresponding THF adduct cation 4b-d(+) along with 1 equiv of the corresponding neutral precursor 2b-d. In contrast, 3a(+) reacts with THF to yield unidentified species. 3a(+) and 3c,d(+)/3c',d'(+) are inactive in ethylene polymerization, but cations 3b-d(+)/3b'-d'(+) polymerize PO with moderate activity to yield low-molecular-weight PPO. [References: 32]
机译：氨基酚2-（CH2L）-6-R-C6H3OH的反应（R = Ph，L = NMe2，1a; R = Bu-t，L = NMe2，1b; R = Bu-t，L = NC4H8，1c ; R = Bu-t，L = NC5H10，1d）与1当量的AlMe3得到相应的二甲基Al络合物{2-（CH2L）-6-R-C6H3O} AlMe2（R = Ph，L = NMe2，2a; R ＝ Bu-t，L ＝ NMe 2，2b; R ＝ Bu-t，L ＝ NC 4 H 8，2c; R ＝ Bu-t，L ＝ NC 5 H 10，2d）高产率。根据对2b，d的X射线分析和对2a-d的NMR数据，化合物2a-d似乎是单体的，并且在THF的存在下是稳定的。 {2-（CH2NMe2）-6-Ph-C6H3O} AlMe2（2a）与B（C6F5）（3）干净反应，生成双核阳离子Al物种3a（+）。 X射线衍射分析表明，阳离子3a（+）可以看作是三配位阳离子{2-（CH2NMe2）-6-Ph-C6H3O} AlMe +和中性前体2a的加合物，其中两个Al中心通过mu（2）-O氨基酚酸酯桥连接。类似地，Al二甲基配合物2b-d与B（C6F5）（3）的反应产生的双核阳离子Al物种3b-d（+）/ 3b'-d'+（3b + / 3b'（+）的比例为1/1比例; 3c，d + / 3c'，d'（+）分别以3/1的比例作为非对映异构体混合物。阳离子3b-d（+）/ 3b'-d'（+）采用与阳离子3a（+）相似的结构，通过X射线晶体学分析3b'（+）和2D NMR研究确定3a（+）。 +）和3c，d + / 3c'，d'+。所有形成的双核阳离子在溶液中都非常稳定且坚固，并且在C6D5Br中，直至80°C都未观察到任何一种的流动行为。阳离子3b-d（+）/ 3b′-d′（+）与路易斯碱如THF反应，得到相应的THF加合物阳离子4b-d（+）以及1当量的相应的中性前体2b-d。相反，3a（+）与THF反应生成未确定的物种。 3a（+）和3c，d（+）/ 3c'，d'（+）在乙烯聚合中不活泼，但阳离子3b-d（+）/ 3b'-d'（+）聚合具有中等活性的PO生成低分子量PPO。 [参考：32]

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