Experimental and computational studies of R3Al-ER '(3) (E = P, As, Sb, Bi; R = Et, t-bu; R ' = SiMe3, i-Pr) donor-acceptor complexes: Role of the central pnictine and the substituents on the structure and stability of alane adducts
Experimental and computational studies of R3Al-ER '(3) (E = P, As, Sb, Bi; R = Et, t-bu; R ' = SiMe3, i-Pr) donor-acceptor complexes: Role of the central pnictine and the substituents on the structure and stability of alane adducts
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R3Al-ER (3) (E = P, As, Sb, Bi;R = Et, t-bu;R = SiMe3, i-Pr) 供体-受体复合物的实验和计算研究：中央 pnictine 的作用
DOI：
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发表时间：
2002
期刊：
影响因子：
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通讯作者：
P. Schreiner
中科院分区：
文献类型：
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作者：
A. Kuczkowski;S. Schulz;M. Nieger;P. Schreiner
在固体状态下，基于单晶X射线结构分析，以及在溶液中通过温度依赖的NMR光谱，研究了Et 3Al-E（SiMe 3）3和t-Bu 3Al-E（i-Pr）3（E = P，As，Sb，Bi）类型的类似取代的刘易斯酸碱加合物中的给体-受体相互作用。此外，进行密度泛函理论计算（B3 LYP/SDD）以分析分子结构并导出R3 Al − ER '3加合物的解离能（De）。它们的热力学稳定性既取决于受中心第13族和第15族元素及其取代基R和R '影响的刘易斯酸和碱的电子强度，又取决于刘易斯酸和碱之间的空间相互作用。这种排斥相互作用是决定性的稳定性的加合物含有小的中心元素，如P和大的取代基，如i-Pr和t-Bu。中心结构参数（Al-E和Al-C（H）键距; C（H）-Al-C（H）键角）和De va之间的比较。
Donor−acceptor interactions within analogously substituted Lewis acid−base adducts of the type Et3Al−E(SiMe3)3 and t-Bu3Al−E(i-Pr)3 (E = P, As, Sb, Bi) were investigated in the solid state, on the basis of single-crystal X-ray structure analyses, and in solution by temperature-dependent NMR spectroscopy. In addition, density functional theory computations (B3LYP/SDD) were performed to analyze molecular structures and to derive dissociation energies (De) of the R3Al−ER‘3 adducts. The thermodynamic stability of these depends both on the electronic strength of the Lewis acid and base, which is influenced by the central group 13 and 15 elements and their substituents R and R‘, and on steric interactions between the Lewis acid and base. Such repulsive interactions are decisive for the stability of adducts containing small central elements such as P and large substituents such as i-Pr and t-Bu. Comparisons between central structure parameters (Al−E and Al−C(H) bond distances; C(H)−Al−C(H) bond angles) and De va...