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A Phosphine‐Coordinated Boron‐Centered Gomberg‐Type Radical
Author(s) -
Rosenthal Amos J.,
Devillard Marc,
Miqueu Karinne,
Bouhadir Ghenwa,
Bourissou Didier
Publication year - 2015
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.201504502
Subject(s) - electron paramagnetic resonance , chemistry , dimer , boron , phosphine , crystallography , hyperconjugation , density functional theory , single crystal , computational chemistry , organic chemistry , nuclear magnetic resonance , molecule , catalysis , physics
The P‐coordinated boryl radical [Ph 2 P(naphthyl)BMes] . (Mes=mesityl) was prepared by (electro)chemical reduction of the corresponding borenium salt or bromoborane. Electron paramagnetic resonance (EPR) analysis in solution and DFT calculations indicate large spin density on boron (60–70 %) and strong P–B interactions (P→B σ donation and B→P negative hyperconjugation). The radical is persistent in solution and participates in a Gomberg‐type dimerization process. The associated quinoid‐type dimer has been characterized by single‐crystal X‐ray diffraction.