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Volumn 127, Issue 10, 2005, Pages 3516-3526

Interaction of a bulky N-heterocyclic carbene ligand with Rh(I) and Ir(I). Double C-H activation and isolation of bare 14-electron Rh(III) and Ir(III) complexes

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVATION ANALYSIS; CARBON; CARBON MONOXIDE; COMPLEXATION; IRRIGATION; PROBABILITY DENSITY FUNCTION;

EID: 14944370682     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja043249f     Document Type: Article
Times cited : (281)

References (80)
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    • Whereas such cyclometalation processes are well-documented and rather common for bulky phosphine and nitrogen-donor ligands, they have been rarely observed in NHCs. An example of intramolecular C-H activation of an NHC on Rh (using the less bulky and less basic IMes ligand) has appeared: Huang, J.; Stevens, E. D.; Nolan, S. P. Organometallics 2000, 19, 1194-1197.
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    • The value found in 2 is similar to values for hydrides trans to O-bound ligands; see: (a) Schrock, R. R.; Osborn, J. A. J. Am. Chem. Soc. 1976, 98, 8, 2134-2142. (b) Rybtchinski, B.; Konstantinovsky, L.; Shimon, L. J. W.; Vigalok, A.; Milstein, D. Chem. Eur. J. 2000, 6, 3287-3292.
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    • Complex 2 can be isolated on a preparative scale by decreasing the reaction time in benzene to 1 h, but contamination by already formed 4 is usually observed.
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    • Dilution is important for the outcome of this reaction. When the reaction is carried out in a more concentrated pentane slurry/solution, the yellow precipitate contains various amounts of 2 (up to 30%).
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    • note
    • 8) show that the spectrum of 5 remains virtually unchanged in the range 297-233 K.
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    • Related examples of proton-hydride interactions involve close contacts between iridium(III) hydrides and a hydrogen atom coordinated to an electronegative heteroatom (O, N). Proton transfer from these acidic hydrogens to Ir-H and formation of iridium dihydrogen complexes have been observed; see: (a) Lough, A. J.; Park, S.; Ramachandran, R.; Morris, R. H. J. Am. Chem. Soc. 1994, 116, 8356-8357. (b) Lee, J. C. Jr.; Peris, E.; Rheingold, A. L.; Crabtree, R. H. J. Am. Chem. Soc. 1994, 116, 11014-11019. For a review on proton-hydride interactions, see: (c) Custelcean, R.; Jackson, J. E. Chem. Rev. 2001, 101, 1963-1980.
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    • Related examples of proton-hydride interactions involve close contacts between iridium(III) hydrides and a hydrogen atom coordinated to an electronegative heteroatom (O, N). Proton transfer from these acidic hydrogens to Ir-H and formation of iridium dihydrogen complexes have been observed; see: (a) Lough, A. J.; Park, S.; Ramachandran, R.; Morris, R. H. J. Am. Chem. Soc. 1994, 116, 8356-8357. (b) Lee, J. C. Jr.; Peris, E.; Rheingold, A. L.; Crabtree, R. H. J. Am. Chem. Soc. 1994, 116, 11014-11019. For a review on proton-hydride interactions, see: (c) Custelcean, R.; Jackson, J. E. Chem. Rev. 2001, 101, 1963-1980.
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    • 0035385141 scopus 로고    scopus 로고
    • Related examples of proton-hydride interactions involve close contacts between iridium(III) hydrides and a hydrogen atom coordinated to an electronegative heteroatom (O, N). Proton transfer from these acidic hydrogens to Ir-H and formation of iridium dihydrogen complexes have been observed; see: (a) Lough, A. J.; Park, S.; Ramachandran, R.; Morris, R. H. J. Am. Chem. Soc. 1994, 116, 8356-8357. (b) Lee, J. C. Jr.; Peris, E.; Rheingold, A. L.; Crabtree, R. H. J. Am. Chem. Soc. 1994, 116, 11014-11019. For a review on proton-hydride interactions, see: (c) Custelcean, R.; Jackson, J. E. Chem. Rev. 2001, 101, 1963-1980.
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    • note
    • Several X-ray structures shown here appear as mirror images of each other. This is due to the fact that they are chiral at the metal center and that an inversion center is imposed upon refinement of their structures.
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    • note
    • In the rhodium case, we observe decomposition to several unidentified products.
  • 57
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    • note
    • These do not give solvent-ligand adducts when dissolved in potentially coordinating solvents such as dichloromethane, THF, or acetone.
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    • NHCs are better donor ligands than alkylphosphines; see ref 13.
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    • note
    • The MO numbering follows the ADF output.
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    • note
    • Evaporation and analysis of the mother liquor show formation of 2 (in addition to free ligand and traces of 1).
  • 67
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    • note
    • Leaving the solution at room temperature for 3 days and subsequent workup result in a mixture of 2 (major) and 4 (minor).
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