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Evidence for Ligand‐Centered Reactivity of a 17e Radical Cationic 2 H ‐Azaphosphirene Complex
Author(s) -
Helten Holger,
Neumann Christoph,
Espinosa Arturo,
Jones Peter G.,
Nieger Martin,
Streubel Rainer
Publication year - 2007
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.200700658
Subject(s) - hexafluorophosphate , chemistry , nitrile , reactivity (psychology) , cationic polymerization , medicinal chemistry , ligand (biochemistry) , stereochemistry , polymer chemistry , organic chemistry , ionic liquid , catalysis , medicine , biochemistry , alternative medicine , receptor , pathology
Reactions of 2 H ‐azaphosphirene complex 1 with electron‐rich nitrile derivatives 2a – e in the presence of substoichiometric amounts of ferrocenium hexafluorophosphate yielded regioselectively 2 H ‐1,4,2‐diazaphosphole complexes 3a – e under mild conditions. The dependence of the reaction on the amount of ferrocenium hexafluorophosphate is discussed. In the reactions of 1 with electron‐poor nitrile derivatives HCN ( 2f ), EtOC(O)CN ( 2g ), and C 6 F 5 CN ( 2h ), byproducts possessing a P–F bond are formed, which indicates that the hexafluorophosphate anion is involved in the reaction course. Apart from NMR spectroscopic ( 3a – f ) and X‐ray data ( 3b , 3d – e ), a detailed DFT study is included that provides first insight into the reaction pathway.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)