Allylic C-H Activation of Olefins by a TpMe2IrIII Compound

作者：Cristobal Crispin; Santos Laura L; Gutierrez Gonzalez Ruben; Alvarez Eleuterio; Paneque Margarita^*; Poveda Manuel L^*

来源：European Journal of Inorganic Chemistry, 2016, 2016(15-16): 2534-2542.

DOI：10.1002/ejic.201501253

• C-H activation
• Iridium
• Scorpionates
• C-C coupling
• Olefination
• Organometallic compounds

The Ir-III compound [Tp(Me2)Ir(C6H5)(2)(N-2)] (1) [Tp(Me2) = hydridotris(3,5-dimethylpyrazolyl)borate] reacts with 1-hexene, propene, -methylstyrene, and 2,3-dimethylbutadiene to yield organometallic products that derive from allylic C-H activations (complexes 3 from 1-hexene, 2 from propene, 5 from -methylstyrene, and 7, 8, and 9 from 2,3-dimethylbutadiene), in all cases along with organic products formed in catalytic (Ir-induced) dehydrogenative coupling of benzene (the solvent of the reaction) and the corresponding olefin, with the latter also acting as the hydrogen scavenger in each case. Differently, complex 1 reacts with (E)--methylstyrene and cyclohexadiene to yield complex 2 and the known ((4)-cyclohexadiene)Ir-I derivative 6, respectively. Finally, compound 1 reacts under mild conditions with cyclopentadiene and methylcyclopentadiene with the generation of phenyl derivatives 11 and 12 in which the corresponding cyclopentadienyl ligand adopts the (5) coordination and forces the Tp(Me2) ligand to coordinate in the (2) mode.

• 出版日期2016-6