Iridium and Rhodium Complexes Containing
Fluorinated Phenyl Ligands and Their Transformation
to η2-Benzyne Complexes, Including the Parent Benzyne
Complex IrCp*(PMe3)(C6H4)
posted on 2002-10-04, 00:00authored byRussell P. Hughes, Roman B. Laritchev, Alex Williamson, Christopher D. Incarvito, Lev N. Zakharov, Arnold L. Rheingold
Treatment of IrCp*(CO)2 (1) with C6F5I in benzene under reflux gives the oxidative addition
product IrCp*(C6F5)(CO)I (2). Treatment of 2 with PMe3 gives IrCp*(C6F5)(PMe3)I (3), which,
on treatment with AgO3SCF3 in the presence of traces of water, affords the cationic complex
[IrCp*(C6F5)(PMe3)(OH2)]O3SCF3 (4). Treatment of 4 with 1,8-bis(dimethylamino)naphthalene (Proton Sponge) affords the hydride complex IrCp*(C6F5)(PMe3)H (5), which reacts with
n-BuLi to give the tetrafluorobenzyne complex IrCp*(η2-C6F4)(PMe3) (6) in high yield.
Similarly, treatment of RhCp*(CO)2 (7) with C6F5I in toluene at 80 °C affords a pentafluorophenyl complex of rhodium, RhCp*(C6F5)(CO)I (8). Treatment of 8 with PMe3 at room
temperature affords RhCp*(C6F5)(PMe3)I (9), which reacts with NaBH4 to give RhCp*(C6F5)(PMe3)H (10). Treatment of 10 with n-BuLi gives the rhodium tetrafluorobenzyne complex
RhCp*(η2-C6F4)(PMe3) (11) in high yield. Treatment of IrCp*(CO)2 with 1-fluoro-2-iodobenzene in toluene under reflux gives the oxidative addition product IrCp*(2-C6FH4)(CO)I (12),
which is converted to IrCp*(2-C6FH4)(PMe3)I (13) by treatment with PMe3. Treatment of 13
with NaBH4 gives IrCp*(2-C6FH4)(PMe3)H (14), which, on treatment with n-BuLi, is
converted to a mixture of the nonfluorinated benzyne complex IrCp*(η2-C6H4)(PMe3) (15)
and the phenyl butyl complex IrCp*(C6H5)(n-Bu)(PMe3) (16). Treatment of Ir(C5Me4Et)(CO)2
with 2,3,4,5-tetrafluorobenzoyl chloride at 110 °C under reflux gives the oxidative addition
product Ir(C5Me4Et)(2,3,4,5-C6F4H)(CO)Cl (17), which on treatment with PMe3 gives Ir(C5Me4Et)(C6F4H)(PMe3)Cl (18). Using analogous methodology this was converted to the
unsymmetrical trifluorobenzyne complex Ir(C5Me4Et)(η2-3,4,5-C6F3H)(PMe3) (21), in which
the benzyne ligand is shown to be stereochemically rigid on the NMR time scale, allowing
a minimum value for the rotational barrier about the iridium−benzyne bond to be estimated
at 20.3 kcal mol-1. The crystal structures of complexes 2, 3, 9, 11−15, 17, and 18 are reported
and discussed, and the “through-space” nature of some coupling constants between 31P, 1H,
and 19F is confirmed using heteronuclear Overhauser enhancement (HOESY) NMR
spectroscopy.