The Aluminum–Nitrogen Bond in Monomeric Bis(amino)alanes: A Systematic Experimental Study of Bis(tetramethylpiperidino)alanes and Quantum Mechanical Calculations on the Model System (H2N)2AlY
The Aluminum–Nitrogen Bond in Monomeric Bis(amino)alanes: A Systematic Experimental Study of Bis(tetramethylpiperidino)alanes and Quantum Mechanical Calculations on the Model System (H2N)2AlY
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单体双(氨基)丙烷中的铝-氮键：双(四甲基哌啶基)丙烷的系统实验研究和模型系统(H2N)2AlY上的量子力学计算
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发表时间：
1998
期刊：
影响因子：
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通讯作者：
T. Seifert
中科院分区：
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作者：
Klaus Knabel;I. Krossing;H. Nöth;Holger Schwenk;M. Schmidt;T. Seifert
金属化亲核试剂M(I)Y [Y = OR， SR, NR2, PR2, AsR2, CR3, Si(SiMe3)3, R = organyl， H]与双（2,2,6,6-四甲基胡椒基）卤化铝[tmp2AlX， （X = Cl, Br， I）]反应，可方便地获得多种双（氨基）al烷tmp2AlY型。通过27al核磁共振光谱、质谱分析和x射线晶体结构测定表明。所有这些compds。在固相、固相和气相中都是单体。即使是不常见的Al-E单键（E = Si， P， As等）也被支持的tmp片段所稳定。系统肛门检查的结果。的键合参数。为tmp2AlY公司。，与量子力学相结合。模型计算机的研究。（H2N）2AlY，不仅揭示了高极性Al-N键的存在，同时也排除了AlN-pp(p)键的存在，这与类似的tmp2BY化合物的情况相反。Al-N键的长度取决于质子HY的酸性特征：d（Al-N）越短，y的碱性越弱[在SciFinder (R)上]
Reactions of metalated nucleophiles M(I)Y [Y = OR, SR, NR2, PR2, AsR2, CR3, Si(SiMe3)3, R = organyl, H] with bis(2,2,6,6-tetramethylpiperidino)aluminum halides [tmp2AlX, (X = Cl, Br, I)] offer facile access to a variety of bis(amino)alanes of the type tmp2AlY. As indicated by 27Al-NMR spectroscopy, mass spectrometry, and x-ray crystal structure detns., all of these compds. are monomeric in the solid state, in soln., and in the gas phase. Even Al-E single bonds (E = Si, P, As etc.) that are not commonly encountered are stabilized by the supporting tmp fragments. The results of a systematic anal. of the bonding parameters detd. for the tmp2AlY compds., combined with a quantum mech. study on model compds. (H2N)2AlY, not only reveal the presence of a highly polar Al-N bond, but at the same time rule out AlN-pp(p) bonding, in contrast to the situation in the analogous tmp2BY compds. The Al-N bond length depends on the acidic character of the protic species HY: the shorter d(Al-N), the less basic is Y. [on SciFinder (R)]