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- W2333897653 abstract "[Fe] hydrogenase (Hmd) catalyzes the heterolytic splitting of H2 by using, in its active site, a unique organometallic iron-guanylylpyridinol (FeGP) cofactor and, as a hydride acceptor, the substrate methenyltetrahydromethanopterin (methenyl-H4MPT+). The combination FeGP/methenyl-H4MPT+ and its reactivity bear resemblance to the concept of frustrated Lewis pairs (FLPs), some of which have been shown to heterolytically activate H2. The present work exploits this interpretation of Hmd reactivity by using the combination of Lewis basic ruthenium metalates, namely K[CpRu(CO)2] (KRp) and a related polymeric Cp/Ru/CO compound (Rs), with the new imidazolinium salt 1,3-bis(2,6-difluorophenyl)-2-(4-tolyl)imidazolinium bromide ([TolImF4]+Br–) that was designed to emulate the hydride acceptor properties of methenyl-H4MPT+. Solid-state structures of [TolImF4]+Br– and the corresponding imidazolidine HTolImF4 reveal that the heterocycle undergoes similar structural changes as in the biological substrate. DFT calculations indicate that heterolytic splitting of dihydrogen by the FLP Rp–/[TolImF4]+ is exothermic, but the formation of the initial Lewis pair should be unfavorable in polar solvents. Consequently the combination Rp–/[TolImF4]+ does not react with H2 but leads instead to side products from nucleophilic substitution (k = 4 × 10–2 L mol –1 s–1 at room temperature). In contrast, the heterogeneous combination Rs/[TolImF4]+ does split H2 heterolytically to give HTolImF4 and HRuCp(CO)2 (HRp) or DTolImF4 and DRp when using D2. The reaction has been followed by 1H/2H and 19F NMR spectroscopy as well as by IR spectroscopy and reaches 96% conversion after 1 d. Formation of HTolImF4 under these conditions demonstrates that superelectrophilic activation by protonation, which has been proposed for methenyl-H4MPT+ to increase its carbocationic character, is not necessarily required for an imidazolinium ion to serve as a hydride acceptor. This unprecedented functional model for the [Fe] hydrogenase, using a Lewis acidic imidazolinium salt as a biomimetic hydride acceptor in combination with an organometallic Lewis base, may provide new inspiration for biomimetic H2 activation." @default.
- W2333897653 created "2016-06-24" @default.
- W2333897653 creator A5012244806 @default.
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- W2333897653 creator A5019958094 @default.
- W2333897653 creator A5057132213 @default.
- W2333897653 creator A5086870920 @default.
- W2333897653 date "2014-11-17" @default.
- W2333897653 modified "2023-10-16" @default.
- W2333897653 title "Functional Model for the [Fe] Hydrogenase Inspired by the Frustrated Lewis Pair Concept" @default.
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- W2333897653 doi "https://doi.org/10.1021/ja509186d" @default.
- W2333897653 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/25353322" @default.
- W2333897653 hasPublicationYear "2014" @default.
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