Metalloradical-Catalyzed Selective 1,2-Rh-H Insertion into the Aliphatic Carbon-Carbon Bond of Cyclooctane

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Authors
Publication date 2015
Journal Organometallics
Volume | Issue number 34 | 12
Pages (from-to) 2849-2857
Organisations
  • Faculty of Science (FNWI) - Van 't Hoff Institute for Molecular Sciences (HIMS)
Abstract The selective aliphatic carboncarbon activation of cyclo-octane (c-octane) was achieved via the Rh-II(ttp)-catalyzed 1,2-addition of Rh(ttp)H to give Rh(ttp)(n-octyl) (ttp = tetratolylporphyrinato dianion) in good yield under mild reaction conditions. This mechanism is further supported by DFT calculations. The reaction worked only with the sterically accessible Rh(ttp) porphyrin complex but not with the bulky Rh(tmp) system (tmp = tetrakismesitylporphyrinato dianion), thus showing the highly steric sensitivity of carboncarbon bond activation by transition metal complexes.
Document type Article
Note With supporting information
Language English
Published at https://doi.org/10.1021/acs.organomet.5b00183
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