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Reactions of α-diimine-aluminum complexes with sodium alkynides: versatile structures of aluminum σ-alkynide complexes†
Dalton Transactions ( IF 3.5 ) Pub Date : 2015-07-06 00:00:00 , DOI: 10.1039/c5dt01693b Yanxia Zhao 1, 2, 3, 4, 5 , Yanyan Liu 1, 2, 3, 4, 5 , Biao Wu 1, 2, 3, 4, 5 , Xiao-Juan Yang 1, 2, 3, 4, 5
Dalton Transactions ( IF 3.5 ) Pub Date : 2015-07-06 00:00:00 , DOI: 10.1039/c5dt01693b Yanxia Zhao 1, 2, 3, 4, 5 , Yanyan Liu 1, 2, 3, 4, 5 , Biao Wu 1, 2, 3, 4, 5 , Xiao-Juan Yang 1, 2, 3, 4, 5
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Reaction of AlCl3 with the monoanionic α-diimine ligand [NaL] yielded the complex [L˙−AlIIICl2−] (1, L = [(2,6-iPr2C6H3)NC(Me)]2), and subsequent reduction of 1 by sodium metal afforded the mononuclear [L2−AlIIICl−(THF)] (2) and binuclear [L2−(THF)AlII−AlII(THF)L2−] (3). Compounds 2 and 3 exhibit interesting reactivities to sodium alkynides at room temperature. Treatment of dialumane 3 with 1 equiv. of 4-methylphenylacetylene in the presence of sodium metal yielded the asymmetric Al–Al-bonded compound [Na(Et2O)][LAl–Al(C![[triple bond, length as m-dash]](https://www.rsc.org/images/entities/char_e002.gif)
C(C6H4–Me))L] (4) containing an alkynyl group attached to one of the Al atoms. The reaction of 2 with 4-methylphenylacetylene and Na (or sodium 4-methylphenylacetylide) resulted in the mononuclear product [L(THF)Al(CC–(C6H4–Me))] (5) containing a single terminal acetylide ligand. Precursor 2 reacted with 2 equiv. of phenylacetylene (or 4-methylphenylacetylene, trimethylsilylacetylene) and Na to give the tweezer “ate” complexes, [Na(THF)(DME)][LAl(CCR)2] (R = C6H5, 6a; C6H4–Me, 6b; Si(Me)3, 6c), [Na(THF)]2[LAl(CCPh)2]2(μ-C7H8) (7), [Na(C7H8)][(μ-Na)][LAl(CCSi(Me)3)2]2 (8), as well as the polymeric [LAl(CCPh)2Na]n (9). In the products, two alkynyl groups coordinate terminally to one Al center and a sodium ion is embedded between these two alkynyls. Interestingly, both cycloaddition and terminal acetylide coordination of three equiv. of alkyne occurred in the reaction of 2 with 1-hexyne, resulting in the unique dialuminum complex [Na(Et2O)]2[{L(C(C4H9)![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
CH)}Al(CC(C4H9))2]2 (10). Complexes 1–10 have been characterized by NMR (1H, 13C) and IR spectroscopy, elemental analysis, and X-ray diffraction, and their electronic structures were studied by DFT calculations.
中文翻译：
α-二亚胺-铝配合物与炔基钠的反应：σ-炔基铝配合物的通用结构†
AlCl 3与单阴离子α-二亚胺配体[NaL]反应，生成配合物[L˙ - Al III Cl 2 - ]（1，L = [（2,6-iPr 2 C 6 H 3）NC（Me）] 2），和随后的还原的1由金属钠，得到单核[L 2-的Al III氯-（THF）]（2）和双核[L 2- （THF）的Al II -Al II（THF）L- 2- ] （3）。化合物2和3在室温下对炔烃钠表现出有趣的反应性。用1当量处理dialumane 3。钠金属存在下，由4-甲基苯基乙炔制得不对称的Al-Al键合化合物[Na（Et 2 O）] [LAl-Al（CC（C 6 H 4 -Me））L]（4）连接到Al原子之一上的炔基。的反应2与4-甲基苯基乙炔和Na（钠或4- methylphenylacetylide）导致单核产物[L（THF）的Al（C C-（C 6 H ^ 4 -Me））]（5）含有单个端乙炔化配体。前体2与2当量反应 苯乙炔（或4-甲基苯基乙炔，三甲基硅烷基）和Na，得到镊子“吃”络合物，[钠（THF）（DME）] [LAL（C CR）2 ]（R = C 6 H ^ 5，图6a ;Ç 6 ħ 4 -Me，6B ;硅（Me）的3，图6c），[钠（THF）] 2 [LAL（C CPH）2 ] 2（μ-C 7 H ^ 8）（7），[钠（C 7 ħ 8）] [（μ-Na）] [LAl（C CSi（Me）3）2 ] 2（8）以及聚合的[LAl（C CPh）2 Na] n（9）。在产物中，两个炔基末端与一个Al中心配位，并且钠离子嵌入这两个炔基之间。有趣的是，环加成和末端乙酰胺配位都为三个当量。2与1-己炔的反应中发生炔烃的缩合反应，生成独特的二铝配合物[Na（Et 2 O）] 2 [{L（C（C 4 H 9）CH）} Al（C C（C 4 H 9））2 ] 2（10）。配合物1–10用NMR（1 H，13 C）和IR光谱，元素分析和X射线衍射对其进行了表征，并通过DFT计算研究了它们的电子结构。
更新日期：2015-07-06
C(C6H4–Me))L] (4) containing an alkynyl group attached to one of the Al atoms. The reaction of 2 with 4-methylphenylacetylene and Na (or sodium 4-methylphenylacetylide) resulted in the mononuclear product [L(THF)Al(CC–(C6H4–Me))] (5) containing a single terminal acetylide ligand. Precursor 2 reacted with 2 equiv. of phenylacetylene (or 4-methylphenylacetylene, trimethylsilylacetylene) and Na to give the tweezer “ate” complexes, [Na(THF)(DME)][LAl(CCR)2] (R = C6H5, 6a; C6H4–Me, 6b; Si(Me)3, 6c), [Na(THF)]2[LAl(CCPh)2]2(μ-C7H8) (7), [Na(C7H8)][(μ-Na)][LAl(CCSi(Me)3)2]2 (8), as well as the polymeric [LAl(CCPh)2Na]n (9). In the products, two alkynyl groups coordinate terminally to one Al center and a sodium ion is embedded between these two alkynyls. Interestingly, both cycloaddition and terminal acetylide coordination of three equiv. of alkyne occurred in the reaction of 2 with 1-hexyne, resulting in the unique dialuminum complex [Na(Et2O)]2[{L(C(C4H9)CH)}Al(CC(C4H9))2]2 (10). Complexes 1–10 have been characterized by NMR (1H, 13C) and IR spectroscopy, elemental analysis, and X-ray diffraction, and their electronic structures were studied by DFT calculations.
中文翻译：
α-二亚胺-铝配合物与炔基钠的反应：σ-炔基铝配合物的通用结构†
AlCl 3与单阴离子α-二亚胺配体[NaL]反应，生成配合物[L˙ - Al III Cl 2 - ]（1，L = [（2,6-iPr 2 C 6 H 3）NC（Me）] 2），和随后的还原的1由金属钠，得到单核[L 2-的Al III氯-（THF）]（2）和双核[L 2- （THF）的Al II -Al II（THF）L- 2- ] （3）。化合物2和3在室温下对炔烃钠表现出有趣的反应性。用1当量处理dialumane 3。钠金属存在下，由4-甲基苯基乙炔制得不对称的Al-Al键合化合物[Na（Et 2 O）] [LAl-Al（C
C（C 6 H 4 -Me））L]（4）连接到Al原子之一上的炔基。的反应2与4-甲基苯基乙炔和Na（钠或4- methylphenylacetylide）导致单核产物[L（THF）的Al（C C-（C 6 H ^ 4 -Me））]（5）含有单个端乙炔化配体。前体2与2当量反应 苯乙炔（或4-甲基苯基乙炔，三甲基硅烷基）和Na，得到镊子“吃”络合物，[钠（THF）（DME）] [LAL（C CR）2 ]（R = C 6 H ^ 5，图6a ;Ç 6 ħ 4 -Me，6B ;硅（Me）的3，图6c），[钠（THF）] 2 [LAL（C CPH）2 ] 2（μ-C 7 H ^ 8）（7），[钠（C 7 ħ 8）] [（μ-Na）] [LAl（C CSi（Me）3）2 ] 2（8）以及聚合的[LAl（C CPh）2 Na] n（9）。在产物中，两个炔基末端与一个Al中心配位，并且钠离子嵌入这两个炔基之间。有趣的是，环加成和末端乙酰胺配位都为三个当量。2与1-己炔的反应中发生炔烃的缩合反应，生成独特的二铝配合物[Na（Et 2 O）] 2 [{L（C（C 4 H 9）CH）} Al（C C（C 4 H 9））2 ] 2（10）。配合物1–10用NMR（1 H，13 C）和IR光谱，元素分析和X射线衍射对其进行了表征，并通过DFT计算研究了它们的电子结构。
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