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首页> 外文期刊>Chemistry: A European journal >tBuP(NH_2)_2-A reactive synthon for the synthesis of molecular imidophosphinates of group 13 metals
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tBuP(NH_2)_2-A reactive synthon for the synthesis of molecular imidophosphinates of group 13 metals

机译：tBuP（NH_2）_2-A反应性合成子，用于合成13族金属的亚氨基次膦酸酯

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摘要

Reactions of tBuP(NH_2)_2 with Group 13 trialkyls MR_3 (M = A1, Ga, In; R = Me, tBu) were investigated in detail. According to variable-temperature (VT) NMR investigations, the reaction proceeds stepwise with the initial formation of aminophosphane ad-ducts, which subsequently react to give iminophosphorane adducts and finally the heterocyclic metallonitridophosphi-nates. BP86/TZVPP (DFT) calculations were performed to verify this reaction pathway, to elucidate the influence of the central Group 13 element on the stability of the reaction intermediates and the heterocycles, as well as to assess the thermodynamics of their formation. The relative stability of free and complexed aminophosphane RP(NH_2)_2 and iminophosphorane R(H_2N)(H)P=NH (adducts) with P~(III) and P~V centers was studied in more detail with DFT and MP2 methods. In addition, the influence of the substitu-ent R was investigated by variation of R from H to Me, tBu, F, and NH_2. In general, the aminophosphane form was found to be favored for the free ligand, however, upon complexation with MR_3 (M = A1, Ga; R = alkyl) both forms are almost equal in energy.
机译：详细研究了tBuP（NH_2）_2与13族三烷基MR_3（M = A1，Ga，In; R = Me，tBu）的反应。根据变温（VT）NMR研究，该反应逐步进行，首先形成氨基膦加合物，然后反应生成亚氨基膦烷加合物，最后生成杂环金属亚膦酸酯。进行BP86 / TZVPP（DFT）计算以验证该反应路径，以阐明13号中心元素对反应中间体和杂环的稳定性的影响，并评估其形成的热力学。用DFT和MP2方法研究了游离和络合的氨基膦RP（NH_2）_2和亚氨基膦R（H_2N）（H）P = NH（加合物）在P〜（III）和P〜V中心的相对稳定性。另外，通过R从H到Me，tBu，F和NH_2的变化来研究取代基R的影响。通常，发现氨基膦烷形式更适合于游离配体，但是与MR_3（M = A1，Ga; R =烷基）络合时，两种形式的能量几乎相等。

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