Journal article
Proton-induced lewis acidity of unsaturated iridium amides
Journal of the American Chemical Society, Vol.128(40), pp.13048-13049
10/11/2006
Handle:
https://hdl.handle.net/2376/116729
PMID: 17017773
Abstract
Oxidation of Cp*Ir((rac-TsDPEN)H (DPEN = H2NCHPhCHPhNTs) with Cp2FePF6 or Ph3CPF6 in MeCN solution generates [Cp*Ir(TsDPEN)(NCMe)]PF6 ([1H(NCMe)]PF6) together with H2 and Ph3CH, respectively. Labeling studies revealed that the Ir-H was abstracted. The formation of a transient electrophilic species is implicated by the formation of a cyclometalated derivative. The labile species [1H(NCMe)]+ was also obtained by protonation of the diamido derivative Cp*Ir(TsDPEN-H) (1) in MeCN solution (BArF4- = B(C6H3-3,5-(CF3)2)4-). The unsaturated, "naked" cation [1H]BArF4 can be prepared by protonation of 1 with H(OEt2)2BArF4 in CH2Cl2 solution or by thermal elimination of MeCN from [1H(NCMe)]+. Crystallographic analysis confirms the structure of this 16e cation in [1H]BArF4. The formally unsaturated species 1 and [1H]BArF4 have strongly contrasting Lewis acidities, with the cation binding PPh3, CO, and NH3. 1 does not measurably bind these same ligands. [1H]BArF4 is reactive toward H2, at least in the absence of inhibiting donor ligands such as MeCN. [1H]BArF4 (CH2Cl2 solutions) catalyzes the addition of H2 to 1 by proton transfer from an apparent dihydrogen complex. This work demonstrates that the protonation activates the Lewis acidity of unsaturated Ir(III) amides, giving rise to novel organometallic Lewis acids.
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Details
- Title
- Proton-induced lewis acidity of unsaturated iridium amides
- Creators
- Zachariah M Heiden - School of Chemical Sciences, University of Illinois, Urbana, 61801, USAThomas B Rauchfuss
- Publication Details
- Journal of the American Chemical Society, Vol.128(40), pp.13048-13049
- Academic Unit
- Chemistry, Department of
- Publisher
- United States
- Identifiers
- 99900547465101842
- Language
- English
- Resource Type
- Journal article