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α‐Radical Phosphines: Synthesis, Structure, and Reactivity
Author(s) -
Gu Lianghu,
Zheng Yiying,
Haldón Estela,
Goddard Richard,
Bill Eckhard,
Thiel Walter,
Alcarazo Manuel
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201704185
Subject(s) - carbene , reactivity (psychology) , chemistry , cationic polymerization , alkyl , single crystal , crystallography , carbon atom , crystal structure , stereochemistry , medicinal chemistry , polymer chemistry , organic chemistry , catalysis , medicine , alternative medicine , pathology
A series of phosphines featuring a persistent radical were synthesized in two steps by condensation of dialkyl‐/diarylchlorophosphines with stable cyclic (alkyl)(amino)carbenes (cAACs) followed by one‐electron reduction of the corresponding cationic intermediates. Structural, spectroscopic, and computational data indicate that the spin density in these phosphines is mainly localized on the original carbene carbon from the cAAC fragment; thus, it remains in the α‐position with respect to the central phosphorus atom. The potential of these α‐radical phosphines to serve as spin‐labeled ligands is demonstrated through the preparation of several Au I derivatives, which were also structurally characterized by single‐crystal X‐ray diffraction.