Phosphorus(III) Cations Supported by a PNP Pincer Ligand and Sub‐Stoichiometric Generation of P4 from Thermolysis of a Nickel Insertion Product |
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Authors: | Dr David E Herbert Adam D Miller Prof Oleg V Ozerov |
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Institution: | Department of Chemistry, Texas A&M University, College Station, TX 77842 (USA) |
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Abstract: | Neutral, mono‐, and dicationic phosphorus(III) compounds are accessible with a supporting PNP pincer ligand (PNP=4‐Me‐2‐iPr2P‐C6H3)2N]). Reaction of (PNP)H with PCl3 and nBu3N furnished (PNP)PCl2 ( 1 ), which displays a highly temperature‐dependent structure in solution. Synthesis and characterization by NMR spectroscopy and X‐ray crystallography of Cl/Br‐scrambled derivatives, a monocationic derivative (PNP)PCl]HCB11H11] ( 4 ), and the dicationic derivatives (PNP)P]OTf]2 ( 5 ), (PNP)P]B(C6F5)4]2 ( 6 ), (PNP)P]B12Cl12] ( 7 ) established that 1 not only undergoes several fluxional processes in solution but also possesses a temperature‐dependent ground state structure. Reaction of 1 with a Ni0 source initially leads to a phosphine–phosphinidene complex, followed by thermal generation of P4. |
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Keywords: | cations ligands nickel NMR spectroscopy phosphorus X‐ray crystallography |
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