Gómez, M., Rendón, N., Álvarez, E., Mereiter, K., Poveda, M. L., & Paneque, M. (2017). Functionalization of 3-Iridacyclopentenes. Chemistry - A European Journal, 23(64), 16346–16356. https://doi.org/10.1002/chem.201703535
E164 - Institut für Chemische Technologien und Analytik
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Journal:
Chemistry - A European Journal
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ISSN:
0947-6539
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Date (published):
16-Nov-2017
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Number of Pages:
11
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Publisher:
WILEY-V C H VERLAG GMBH
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Peer reviewed:
Yes
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Keywords:
C=C reactivity; Wolff rearrangement; iridium; metallacycles; ring contraction
en
Abstract:
Members of a series of iridacyclopentenes of composition [TpMe2 Ir(k2 -C,C-CH2 CR'=CRCH2 )(CO)] (TpMe2 =hydrotris(3,5-dimethylpyrazolyl)borate; R=R'=H, 1; R=Me, R'=H, 2; R=R'=Me, 3) have been subjected to common organic chemistry procedures for hydrogenation, cyclopropanation, epoxidation, water addition through hydroboration, cis-dihydroxylation, and ozonolysis. The stability of metallacycles 1-3, imparted by the presence of the co-ligands TpMe2 and CO, directs the reactivity towards the C=C double bonds, and furthermore the stereochemistry of the products formed is strongly dictated by the steric demands of the TpMe2 ligand. While the products obtained in some of the above-mentioned reactions are the expected ones from an organic chemistry point of view, in other cases the results differ from the outcomes of similar reactions carried out with the all-carbon counterparts.
