A new class of chelating N-heterocyclic carbene ligands and their complexes with palladium

Organometallics

Volumn 23, Issue 13, 2004, Pages 3105-3107

  Waltman, Andrew W ^a   Grubbs, Robert H ^a  

^a CALIFORNIA INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ARYL GROUPS; CARBENES; LIGANDS; RUTHENIUM COMPLEXES;

AROMATIC COMPOUNDS; CATALYSIS; CATALYSTS; CHELATION; CRYSTALLOGRAPHY; HYDROGEN; PALLADIUM; PHENOLS; SYNTHESIS (CHEMICAL);

ORGANOMETALLICS;

EID: 3042740597     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om049727c     Document Type: Article

References (38)

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24. During preparation of this paper, a synthesis very similar to this one was reported: Dinger, M. B.; Nieozypor, P.; Mol, J. C. Organometallica 2003, 22, 5291-5296. See also: Lambert, J. B.; Huseland, D. E.; Wang, G.-T. Synthesis 1988, 657-658.
25. During preparation of this paper, a synthesis very similar to this one was reported: Dinger, M. B.; Nieozypor, P.; Mol, J. C. Organometallica 2003, 22, 5291-5296. See also: Lambert, J. B.; Huseland, D. E.; Wang, G.-T. Synthesis 1988, 657-658.
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28. 6) of carbene precursor 4d treated with 2 equiv of KHMDS features a resonance at 238.8 ppm (compare to 8d, where the carbene carbon appears at 197.4 ppm), which is in accordance with the reported chemical shift of the carbene carbon of a potassium carbene complex; see: Alder, R. W.; Blake, M. E.; Bortolotti, C.; Bufali, S.; Butts, C. P.; Linehan, E.; Oliva, J. M.; Orpen, A. G.; Quayle, M. J. Chem. Commun. 1999, 241-242. However, a very high downfield shift may also be indicative of an uncoordinated NHC in solution; see: Arduengo, A. J.; Harlow, R. L.; Kline, M. J. Am. Chem. Soc. 1991, 113, 361-363. Because there is likely a potassium ion associated with the anionic phenoxide moiety, it seems probable that the product of two successive deprotonations of 4d is a potassium carbene complex, although the exact nature of this species is unknown. Investigations into the precise structure are currently underway.
29. 6) of carbene precursor 4d treated with 2 equiv of KHMDS features a resonance at 238.8 ppm (compare to 8d, where the carbene carbon appears at 197.4 ppm), which is in accordance with the reported chemical shift of the carbene carbon of a potassium carbene complex; see: Alder, R. W.; Blake, M. E.; Bortolotti, C.; Bufali, S.; Butts, C. P.; Linehan, E.; Oliva, J. M.; Orpen, A. G.; Quayle, M. J. Chem. Commun. 1999, 241-242. However, a very high downfield shift may also be indicative of an uncoordinated NHC in solution; see: Arduengo, A. J.; Harlow, R. L.; Kline, M. J. Am. Chem. Soc. 1991, 113, 361-363. Because there is likely a potassium ion associated with the anionic phenoxide moiety, it seems probable that the product of two successive deprotonations of 4d is a potassium carbene complex, although the exact nature of this species is unknown. Investigations into the precise structure are currently underway.
30. 6) of carbene precursor 4d treated with 2 equiv of KHMDS features a resonance at 238.8 ppm (compare to 8d, where the carbene carbon appears at 197.4 ppm), which is in accordance with the reported chemical shift of the carbene carbon of a potassium carbene complex; see: Alder, R. W.; Blake, M. E.; Bortolotti, C.; Bufali, S.; Butts, C. P.; Linehan, E.; Oliva, J. M.; Orpen, A. G.; Quayle, M. J. Chem. Commun. 1999, 241-242. However, a very high downfield shift may also be indicative of an uncoordinated NHC in solution; see: Arduengo, A. J.; Harlow, R. L.; Kline, M. J. Am. Chem. Soc. 1991, 113, 361-363. Because there is likely a potassium ion associated with the anionic phenoxide moiety, it seems probable that the product of two successive deprotonations of 4d is a potassium carbene complex, although the exact nature of this species is unknown. Investigations into the precise structure are currently underway.
31. 6) of carbene precursor 4d treated with 2 equiv of KHMDS features a resonance at 238.8 ppm (compare to 8d, where the carbene carbon appears at 197.4 ppm), which is in accordance with the reported chemical shift of the carbene carbon of a potassium carbene complex; see: Alder, R. W.; Blake, M. E.; Bortolotti, C.; Bufali, S.; Butts, C. P.; Linehan, E.; Oliva, J. M.; Orpen, A. G.; Quayle, M. J. Chem. Commun. 1999, 241-242. However, a very high downfield shift may also be indicative of an uncoordinated NHC in solution; see: Arduengo, A. J.; Harlow, R. L.; Kline, M. J. Am. Chem. Soc. 1991, 113, 361-363. Because there is likely a potassium ion associated with the anionic phenoxide moiety, it seems probable that the product of two successive deprotonations of 4d is a potassium carbene complex, although the exact nature of this species is unknown. Investigations into the precise structure are currently underway.
32. 2 (65.4 mg, 0.12 mmol, 0.5 equiv) in THF (5 mL) was added. The resulting yellow suspension quickly became a light yellow solution with a fine precipitate. It was stirred at room temperature for 1 h and then filtered through Celite. The solvent was then removed under reduced pressure until ca. 1 mL remained. To this was added pentane, and the resulting suspension was allowed to stand at -40°C overnight. After 12 h, the product, a beige solid, was collected by filtration (39 mg, 0.08 mmol, 32% yield).
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36. 6.
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