Abstract
The chemistry of phosphaalumenes [R–Al=P–R’] featuring multiple bonds between phosphorus and aluminum remains largely unexplored. Here we show the syntheses of a phosphaalumene(3) through either the reaction of DippNacNacM (DippNacNac = HC[(CMe)N(2,6-iPr2C6H3)]2, M = Al) with a bisphosphirane-fused anthracene (1) or with a phospha-Wittig reagent (2) under mild conditions. This phosphaalumene exhibits reactivities that stand in contrast to those of previously reported transient species II, especially in its ability to activate small molecules such as dihydrogen (H2), white phosphorus (P4), isocyanides, CO2, N2O, trimethylsilyl azide (TMSN3), diphenyl diselenide (PhSeSePh), PhSiH3, PhNH2, styrene and 1-ethynyl-4-methylbenzene. It has been found in this research that the ligand environment can have a subtle but profound impact on the reactivity of phosphaalumenes.
Data availability
All data generated or analyzed during this study are included in the Supplementary Information. Details about materials and methods, experimental procedures, characterization data, and theoretical calculations are available in the Supplementary Information. The structures of 2–13 and 15–19 in the solid state were determined by single-crystal X-ray diffraction studies and the crystallographic data have been deposited with the Cambridge Crystallographic Data Center under nos. CCDC 2455485 (2), 2455483 (3), 2455486 (4), 2455481 (5), 2475851 (6), 2455482 (7), 2503430 (8), 2455480 (9), 2455487 (10), 2475850 (11), 2475849 (12), 2503426 (13), 2503427(15), 2455479 (16), 2455484 (17), 2503429 (18), and 2503428 (19). These data can be obtained free of charge from the Cambridge Crystallographic Data Center via www.ccdc.cam.ac.uk/data request/cif. All data are also available from corresponding authors upon request. Source data are provided with this paper.
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This work was supported by the National Natural Science Foundation of China (22471177), the Sichuan Science and Technology Program (2024NSFSC0285, 2022ZYD0050), the Funding for Hundred Talent Program of Sichuan University (YJ2021161), and the Fundamental Research Funds for the Central Universities. We would like to thank Dr. Yongxin Li (NTU) and Meng Yang (Sichuan University) for support in Single-crystal X-ray diffraction analysis. We acknowledge Dongyan Deng and Jing Li at Sichuan University, and Qianli Li at Liaocheng University for assistance in NMR and HRMS measurement. We thank Dr. William C. Ewing (VanDeMark) for his kind support on the preparation of the manuscript.
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Y.C., X.Z. F.L. X.N., T.L., and Q.L. carried out the experiment work. Z.Y. and P.G. conducted theoretical studies. W.L. conceived and supervised the study. Y.C., Z.Y., and W.L. drafted the manuscript. All authors contributed to discussions.
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Cha, Y., Yang, Z., Zhuang, X. et al. An isolable phosphaalumene(3) capable of small molecule activation via unique modes of reactivity. Nat Commun (2026). https://doi.org/10.1038/s41467-026-69118-4
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DOI: https://doi.org/10.1038/s41467-026-69118-4
