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Reactivity of Aromatic Phosphorus Heterocycles – Differences Between Nonfunctionalized and Pyridyl‐Substituted 2,4,6‐Triarylphosphinines
Author(s) -
Pfeifer Gregor,
Ribagnac Philippe,
Le Goff XavierFrédéric,
Wiecko Jelena,
Mézailles Nicolas,
Müller Christian
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201403048
Subject(s) - chemistry , reactivity (psychology) , sulfur , solvent , nuclear magnetic resonance spectroscopy , phosphorus , methanol , organic chemistry , aromaticity , crystal structure , single crystal , medicinal chemistry , molecule , crystallography , medicine , alternative medicine , pathology
Detailed studies on the reactivity of 2‐(2′‐pyridyl)‐4,6‐diphenylphosphinine ( 2 ) towards CF 3 SO 3 H and sulfur have been performed, and the results were compared with those for nonfunctionalized 2,4,6‐triphenylphosphinine derivatives. Substantial differences between these heterocycles were observed, and the reaction products could be characterized crystallographically. The reactions of 2,4,6‐triarylphosphinine sulfides with methanol led to different products, which could be characterized by NMR spectroscopy and X‐ray crystal structure analysis. Interestingly, the outcomes of these transformations strongly depend on the presence of an additional donor functionality within the phosphorus heterocycle as well as the nature of the solvent and the reaction temperature. DFT calculations were performed to rationalize the different reaction pathways.