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. 2025 Feb 25;54(9):3827-3832.
doi: 10.1039/d4dt03397c.

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

Yi Ding  1 , Yinghua Ma  1 , Yongheng Tang  1 , Yang Fu  1 , Jiayi Wan  1 , Zhiyuan Xu  1 , Yifei He  1 , Zhenhai Shi  1 , Mohd Nazish  2 , Peng Wu  1 , Herbert W Roesky  3
Affiliations

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

Yi Ding et al. Dalton Trans. .

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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