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Single and Double CCl‐Activation of Methylene Chloride by P,N‐ligand Coordinated Rhodium Complexes
Author(s) -
Blank Benoît,
Glatz Germund,
Kempe Rhett
Publication year - 2009
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.200800359
Subject(s) - rhodium , methylene , chloride , ligand (biochemistry) , chemistry , medicinal chemistry , stereochemistry , catalysis , organic chemistry , receptor , biochemistry
Two in one : The simultaneous formation of bimetallic μ‐methylene bridged Rh III complexes as well as dimeric Rh III complexes with terminal chloromethyl groups is observed for P,N‐ligand stabilized Rh I complexes by CCl bond activation of methylene chloride. A mechanistic proposal for the formation of both activation products is also discussed.The synthesis of Rh I complexes with P‐functionalized aminopyridine ligands is reported as well as the first simultaneous observation of a single and double activation of CCl bonds of methylene chloride affording both a dimeric Rh III complex bearing terminal CH 2 Cl groups in addition to a binuclear Rh III complex with a bridging μ‐CH 2 group. The structures of the oxidative addition products were obtained by X‐ray diffraction studies and NMR experiments were performed to elucidate some aspects of the reaction pathway.