Abstract
In contrast to the well-established transition-metal-mediated activation of white phosphorus (P4), the metal-free direct functionalization of P4 has remained rare. The conversion of P4 into a reactive zero-valent diphosphorus compound (P2) has proven challenging to carry out without relying on metal reactivity. Herein, we describe the facile degradation of P4 mediated by two divalent silicon atoms in a bis(silylene) scaffold, resulting in a silylene-stabilized zero-valent P2 complex. The presence of two lone pairs of electrons on each P atom in the silylene-stabilized P2 complex enables a rich reactivity towards small molecules; reaction of the P2 species with CO2, water or a borane leads to the formation of P–C, P–H or P–B bonds, respectively. Notably, the P2 complex also serves as a single phosphorus anion (P−) transfer reagent towards metal carbonyls and a chlorogermylene compound, leading to the synthetically valuable phosphaketenide (PCO−) ligand and a phosphinidene germylene complex, respectively.
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Data availability
Crystallographic data for the structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 1978612 (2), 1978615 (3), 1978613 (4), 1978616 (5), 1978614 (6), 1978617 (7), 1978618 (8), 1978619 (9), 1978620 (10). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. All other data supporting the findings of this study are available within the Article, its Supplementary Information and from the corresponding author upon reasonable request.
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Acknowledgements
We thank P. Nixdorf for assistance with the X-ray diffraction measurements. This work was financially supported by the Deutsche Forschungsgemeinschaft (DR 226/19-2) (Germany’s Excellence Strategy−EXC 2008/1-390540038 (UniSysCat)). Y.W. acknowledges financial support from the China Scholarship Council.
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M.D. and Y.W. conceived and designed the experiments. Y.W. carried out the synthetic experiments and analysed the experimental data. T.S. performed the theoretical calculations. Y.W. and S.Y. conducted the crystallographic studies. M.D., Y.W. and T.S. wrote the manuscript. M.D. supervised the study. All authors discussed the results and commented on the manuscript.
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Extended data
Extended Data Fig. 1 Natural Resonance Theory analysis for the surrogates of A, B and 2.
a, Natural Resonance Theory analysis for surrogate of A. Bulky substituents of the cAAC ligand are replaced by hydrogens. Resonance structures with more than 1 weight percent is shown. b, Natural Resonance Theory analysis for surrogate of B. Bulky substituents of the NHC ligand are replaced by hydrogens. No covalent reference structure was found thus NRT analysis was not successful and these results could implicitly point to the importance of donor-acceptor reference structure. c, Natural Resonance Theory analysis for surrogate of 2. Ph and tBu substituents of the amidinate ligand are replaced by hydrogens and the xanthene backbone were replaced by two methyl groups. No covalent reference structure was found thus NRT analysis was not successful and these results could implicitly point to the importance of donor-acceptor reference structure.
Extended Data Fig. 2 DFT-derived mechanism of P4 activation by 1 leading to 2.
In the initial step, the lone pair of electrons at one silylene group induce the cage-opening in P4 to give the intermediate D. Then, the other silylene moiety in 1 interacts with the P = P bond affording compound E, which can further react with one molecule of 1 to form the branched intermediate F. As bis(silylene) 1 involves another reactive silylene moiety in close proximity, the reaction can go further to fragment the P4 moiety resulting in the bis(NHSi)-supported P2 complex 2.
Supplementary information
Supplementary Information
General considerations, synthetic procedures, compound characterization data including spectroscopic and analytical data for all new compounds, NMR spectra, single-crystal X-ray crystallographic data, computational details containing Cartesian coordinates of computational structures, Supplementary Figs. 1–54, Tables 1–45 and references 1–11.
Supplementary Data 1
CIF for compound 2; CCDC reference: 1978612.
Supplementary Data 2
CIF for compound 3; CCDC reference: 1978615.
Supplementary Data 3
CIF for compound 4; CCDC reference: 1978613.
Supplementary Data 4
CIF for compound 5; CCDC reference: 1978616.
Supplementary Data 5
CIF for compound 6; CCDC reference: 1978614.
Supplementary Data 6
CIF for compound 7; CCDC reference: 1978617.
Supplementary Data 7
CIF for compound 8; CCDC reference: 1978618.
Supplementary Data 8
CIF for compound 9; CCDC reference: 1978619.
Supplementary Data 9
CIF for compound 10; CCDC reference: 1978620.
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Wang, Y., Szilvási, T., Yao, S. et al. A bis(silylene)-stabilized diphosphorus compound and its reactivity as a monophosphorus anion transfer reagent. Nat. Chem. 12, 801–807 (2020). https://doi.org/10.1038/s41557-020-0518-0
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DOI: https://doi.org/10.1038/s41557-020-0518-0
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