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Full Paper
Phosphorus(III) Cations Supported by a PNP Pincer Ligand and Sub-Stoichiometric Generation of P4 from Thermolysis of a Nickel Insertion Product
Article first published online: 24 MAY 2012
DOI: 10.1002/chem.201103981
Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Additional Information
How to Cite
Herbert, D. E., Miller, A. D. and Ozerov, O. V. (2012), Phosphorus(III) Cations Supported by a PNP Pincer Ligand and Sub-Stoichiometric Generation of P4 from Thermolysis of a Nickel Insertion Product. Chem. Eur. J., 18: 7696–7704. doi: 10.1002/chem.201103981
Publication History
- Issue published online: 13 JUN 2012
- Article first published online: 24 MAY 2012
- Manuscript Received: 19 DEC 2011
Funded by
- Welch Foundation
- National Science Foundation. Grant Number: CHE-0755207
Keywords:
- cations;
- ligands;
- nickel;
- NMR spectroscopy;
- phosphorus;
- X-ray crystallography
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.