Rollover Cyclometalation Pathway in Rhodium Catalysis: Dramatic NHC Effects in the C-H Bond Functionalization

Cited 116 time in webofscience Cited 0 time in scopus
  • Hit : 471
  • Download : 0
Organometallic chelates are readily obtained upon coordination of metal species to multidentate ligands. Because of the robust structural nature, chelation frequently serves as a driving force in the molecular assembly and chemical architecture, and they are used also as an efficient catalyst in numerous reactions. Described herein is the development of a Rh(NHC) catalytic system for the hydroarylation of alkenes and alkynes with 2,2'-bipyridines (bipy) and 2,2'-biquinolines; the most representative chelating molecules. Initially generated (bipy)Rh(NHC) chelates become labile because of the strong trans-effect of N-heterocyclic carbenes, thus weakening a rhodium-pyridyl bond, which is trans to the bound NHC. Subsequent rollover cyclometalation leads to the C-H bond activation, eventually giving rise to double functionalization of chelate molecules. Density functional calculations are in good agreement with our mechanistic proposal based on the experimental data. The present study elucidated for the first time the dramatic NHC effects on the rollover cyclometalation pathway enabling highly efficient and selective bisfunctionalization of 2,2'-bipyridines and 2,2'-biquinolines.
Publisher
AMER CHEMICAL SOC
Issue Date
2012-10
Language
English
Article Type
Article
Keywords

TRANSITION-METAL-COMPLEXES; N-HETEROCYCLIC CARBENES; CARBON-HYDROGEN BONDS; DIRECT ARYLATION; ORTHO-ALKYLATION; AROMATIC IMINES; (S)-3,3' -DIMETHYL-2,2' -BIQUINOLINE N,N' -DIOXIDE; INTRAMOLECULAR ACTIVATION; PLATINUM(II) DERIVATIVES; PHOTOPHYSICAL PROPERTIES

Citation

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.134, no.42, pp.17778 - 17788

ISSN
0002-7863
DOI
10.1021/ja308205d
URI
http://hdl.handle.net/10203/102684
Appears in Collection
EEW-Journal Papers(저널논문)CH-Journal Papers(저널논문)
Files in This Item
There are no files associated with this item.
This item is cited by other documents in WoS
⊙ Detail Information in WoSⓡ Click to see webofscience_button
⊙ Cited 116 items in WoS Click to see citing articles in records_button

qr_code

  • mendeley

    citeulike


rss_1.0 rss_2.0 atom_1.0