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Iridium complexes of the conformationally rigid IBioxMe4Ligand : hydride complexes and dehydrogenation of cyclooctene
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Hauser, Simone A., Tonner, Ralf and Chaplin, Adrian B. (2015) Iridium complexes of the conformationally rigid IBioxMe4Ligand : hydride complexes and dehydrogenation of cyclooctene. Organometallics, 34 (17). pp. 4419-4427. doi:10.1021/acs.organomet.5b00658 ISSN 0276-7333.
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Official URL: http://dx.doi.org/10.1021/acs.organomet.5b00658
Abstract
A method for accessing the formally 14 VE iridium(III) hydride fragment {Ir(IBioxMe4)2(H)2}+ (2), containing the conformationally rigid NHC ligand IBioxMe4, is reported. Hydrogenation of trans-[Ir(IBioxMe4)2(COE)Cl] (1) in the presence of excess Na[BArF4] leads to the formation of dimeric [{Ir(IBioxMe4)2(H)2}2Cl][BArF4] (3), which is structurally fluxional in solution and acts as a reservoir of monomeric 2 in the presence of excess halogen ion abstractor. Stable dihydride complexes trans-[Ir(IBioxMe4)2(2,2′-bipyridine)(H)2][BArF4] (4) and [Ir(IBioxMe4)3(H)2][BArF4] (5) were subsequently isolated through in situ trapping of 2 using 2,2′-bipyridine and IBioxMe4, respectively, and fully characterized. Using mixtures of 3 and Na[BArF4] as a latent source of 2, the reactive monomeric fragment’s reactivity was explored with excess ethylene and cyclooctene, and trans-[Ir(IBioxMe4)2(C2H4)2][BArF4] (6) and cis-[Ir(IBioxMe4)2(COD)][BArF4] (7) were isolated, respectively, through sacrificial hydrogenation of the alkenes. Complex 6 is notable for the adoption of a very unusual orthogonal arrangement of the trans-ethylene ligands in the solid state, which has been analyzed computationally using energy and charge decomposition (EDA-NOCV). The formation of 7 via transfer dehydrogenation of COE highlights the ability to partner IBioxMe4 with reactive metal centers capable of C–H bond activation, without intramolecular activation. Reaction of 7 with CO slowly formed trans-[Ir(IBioxMe4)2(CO)2][BArF4] (8), but the equivalent reaction with bis-ethylene 6 was an order of magnitude faster, quantifying the strong coordination of COD in 7.
| Item Type: | Journal Article | ||||||
|---|---|---|---|---|---|---|---|
| Subjects: | Q Science > QD Chemistry | ||||||
| Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||
| Library of Congress Subject Headings (LCSH): | Dehydrogenation, Cycloalkenes , Iridium | ||||||
| Journal or Publication Title: | Organometallics | ||||||
| Publisher: | American Chemical Society | ||||||
| ISSN: | 0276-7333 | ||||||
| Official Date: | 2 September 2015 | ||||||
| Dates: |
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| Volume: | 34 | ||||||
| Number: | 17 | ||||||
| Page Range: | pp. 4419-4427 | ||||||
| DOI: | 10.1021/acs.organomet.5b00658 | ||||||
| Status: | Peer Reviewed | ||||||
| Publication Status: | Published | ||||||
| Access rights to Published version: | Restricted or Subscription Access | ||||||
| Date of first compliant deposit: | 8 November 2016 | ||||||
| Date of first compliant Open Access: | 8 November 2016 | ||||||
| Funder: | Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung [Swiss National Science Foundation] (SNSF), Royal Society (Great Britain), University of Warwick, University of Warwick Institute of Advanced Study Scholarship |
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