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Stoichiometric and Catalytic Reactions Involving Si−H Bond Activations by Rh and Ir Complexes Containing a Pyridylindolide Ligand
| Content Provider | Semantic Scholar |
|---|---|
| Author | Karshtedt, Dmitry Bell, Alexis T. Tilley, T. Don |
| Copyright Year | 2006 |
| Abstract | New rhodium and iridium complexes containing the bidentate, monoanionic 2-(2'-pyridyl)indolide (PyInd) ligand were prepared. The bis(ethylene) complex (PyInd)Rh(C2H4)2 (3) reacted with triethylsilane at 60 °C to produce the 16-electron Rh(V) bis(silyl)dihydride complex (PyInd)RhH2(SiEt3)2 (4). Both 3 and 4 catalyzed the chloride transfer reaction of chlorobenzene and Et3SiH to give Et3SiCl and benzene in the absence of base. In the presence of LiNiPr2, catalytic C−Si coupling was observed, to produce Et3SiPh. Analogous Ir complexes of the type (PyInd)IrH2(SiR3)2, where R3 = Et3 (6a), Me2Ph (6b), Ph2Me (6c), or Ph3 (6d), were not catalytically active in this chloride transfer chemistry. The molecular structure of 6c, determined by X-ray crystallography, may be described as having a highly unusual bicapped tetrahedral geometry. DFT calculations indicate that this distortion is associated with the d4 electron count and the presence of highly trans-influencing silyl ligands. The reaction of 6a with PMe3 (5 eq... |
| Starting Page | 4471 |
| Ending Page | 4482 |
| Page Count | 12 |
| File Format | PDF HTM / HTML |
| Volume Number | 25 |
| Alternate Webpage(s) | http://www.cchem.berkeley.edu/atbgrp/files/Organometallics%202006%2025%204471.pdf |
| Alternate Webpage(s) | https://doi.org/10.1021/om060492%2B |
| Language | English |
| Access Restriction | Open |
| Content Type | Text |
| Resource Type | Article |
