The divergent reactivity of β-diketiminato aluminium hydrides with organophosphoryl compounds†

IF 3.3 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions Pub Date : 2025-01-22 DOI:10.1039/D4DT03397C

Yi Ding, Yinghua Ma, Yongheng Tang, Yang Fu, Jiayi Wan, Zhiyuan Xu, Yifei He, Zhenhai Shi, Mohd Nazish, Peng Wu and Herbert W. Roesky

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Abstract

The reactions of LAlH₂ (L = HC(CMeNAr)₂, Ar = 2,6-ⁱPr₂C₆H₃) (1) with diphenylphosphane oxide [Ph₂P(O)H], diphenylphosphinamide [Ph₂P(O)NH₂], and diaryl/alkyl phosphane [(RO)₂P(O)H (R = Ph, or ⁱPr)] afford their corresponding compounds with compositions LAl(H)OP(Ph)₂ (2), LAl[OP(Ph)₂]₂ (3), LAl{[N(H)P(O)(Ph)₂][OP(Ph)₂]} (4), LAl(OⁱPr)₂ (5), and LAl(OPh)₂ (6), respectively. These reactions probably undergo a process of dehydrogenation coupling, deaminating dehydrogenation coupling, or chain-breaking coupling. It is noteworthy to mention that the reaction of compound 1 with 2 equiv. of Ph₂P(O)NH₂ results in 4 and its isomer 4a, where both the complexes exhibit different coordination towards the aluminium centre. The structure of 4a is very rare, where the aluminium centre connects with a nacnac ligand as well as with N and O to form a six-membered and a four-membered ring, respectively. All the compounds were well characterized by multinuclear NMR spectroscopy, elementary analysis, and single-crystal X-ray diffraction.

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β-二氯胺酮氢化铝与有机磷基化合物的发散反应性

LAlH2 (L = HC(CMeNAr)2, Ar = 2,6- ipr2c6h3)(1)与二苯基膦氧化物[Ph2P(O)H]、二苯基膦酰胺[Ph2P(O)NH2]和二芳基/烷基膦[(RO)2P(O)H (R = Ph或iPr)]反应生成相应的化合物，分别为LAl(H)OP(Ph)2(2)、LAl[OP(Ph)2]2(3)、LAl{[N(H)P(O)(Ph)2][OP(Ph)2]}(4)、LAl(OiPr)2(5)和LAl(OPh)2(6)。这些反应可能经历脱氢偶联、脱氨脱氢偶联或断链偶联过程。值得注意的是，化合物1与2等量的Ph2P(O)NH2反应生成4及其同分异构体4a，这两种配合物对铝中心的配位不同。4a的结构非常罕见，其中铝中心与Nacnac配体以及与N和O连接，分别形成一个六元环和一个四元环。所有化合物均通过多核磁共振谱、元素分析和单晶x射线衍射进行了表征。

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来源期刊

Dalton Transactions 化学-无机化学与核化学

CiteScore

6.60

自引率

7.50%

发文量

1832

审稿时长

1.5 months

期刊介绍： Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.