Double C-H Activation in a Rh-NHC Complex Leading to the Isolation of a 14-Electron Rh(III) Complex

Journal of the American Chemical Society

Volumn 126, Issue 16, 2004, Pages 5054-5055

  Dorta, Reto ^a   Stevens, Edwin D ^a   Nolan, Steven P ^a  

^a UNIVERSITY OF NEW ORLEANS   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CARBENOID; HETEROCYCLIC COMPOUND; METAL COMPLEX; RUBIDIUM;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL BOND; CHEMICAL REACTION; COMPLEX FORMATION; HYDROGEN BOND; MOLECULAR INTERACTION; REACTION ANALYSIS;

EID: 1942456877     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja049545+     Document Type: Article

References (33)

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23. 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.
24. 8). On the other hand, heating at 323 K for 15 min leads to extensive H/D scrambling between the deuterated solvent and complex 2. More detailed studies will be presented elsewhere.
25. Indeed, complex 2 can be isolated on a preparative scale by decreasing the reaction time to 1 h, but contamination by already formed 3 is usually observed.
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29. More detailed experimental and computational work is underway to determine the most likely pathway for this transformation.
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31. Double cyclometalation on an Ir-PCP system has been investigated: Mohammad, H. A. Y.; Grimm, J. C.; Eichele, K.; Mack, H.-G.; Speiser, B.; Novak, F.; Quintanilla, M. G.; Kaska, W. C.; Mayer, H. A. Organometallics 2002, 21, 5775-5784.
32. An X-ray study of 1 has been carried out and will be published.
33. Distances between the metal center and the adjacent tert-butyl groups are outside the range of weak agostic interactions involving Rh complexes, see ref 14 and: Neve, F.; Ghedini, M.; Crispini, A. Organometallics 1992, 11, 3324-3327.