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Allylic C–H Activation of Olefins by a TpMe2IrIII Compound
Author(s) -
Cristóbal Crispín,
Santos Laura L.,
GutiérrezGonzález Rubén,
Álvarez Eleuterio,
Paneque Margarita,
Poveda Manuel L.
Publication year - 2016
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201501253
Subject(s) - chemistry , allylic rearrangement , ligand (biochemistry) , medicinal chemistry , cyclopentadienyl complex , olefin fiber , propene , catalysis , cyclopentadiene , yield (engineering) , derivative (finance) , photochemistry , stereochemistry , organic chemistry , biochemistry , materials science , receptor , economics , financial economics , metallurgy
The Ir III compound [Tp Me2 Ir(C 6 H 5 ) 2 (N 2 )] ( 1 ) [Tp Me2 = hydridotris(3,5‐dimethylpyrazolyl)borate] reacts with 1‐hexene, propene, α‐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 α‐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 )‐β‐methylstyrene and cyclohexadiene to yield complex 2 and the known (η 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 η 5 coordination and forces the Tp Me2 ligand to coordinate in the κ 2 mode.