Addition and NN bond cleavage of diazo-compounds by phosphino-phosphenium cations

Literature Information

Publication Date 2023-12-21
DOI 10.1039/D3CC05728C
Impact Factor 6.222
Authors

Hyehwang Kim, Alan Lough, Zheng-wang Qu, Stefan Grimme


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Abstract

The phosphino-phosphenium cation (PPC) [Ph3PPPh2][GaCl4] reacts as a frustrated Lewis pair to add across the NN bond of (tBuO2CN)2. In contrast, photolytical addition [Ph2ClPPPh2][GaCl4] to (RN)2 results in cleavage of the NN bond affording [Ph2P(μ-NR)2PPh2Cl][GaCl4] (R = Ph 2, C6H4Cl3). While the chloride of 2 is replaced with N3 or CN via reaction with Me3SiN3 or tBuNC respectively, reaction with (C6F5)2BH effects ring opening to give [HN(Ph)PPh2(μ-NPh)PPh2][GaCl4] 7. This reactivity demonstrates that PPCs behave as FLPs to effect either addition or cleavage of NN double bonds.

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