Density functional study of protonated formylmetallocenes

article Density functional study of protonated formylmetallocenes published yes Anđela Šarić author bf63d406-f056-11eb-b41d-f263a6566d8b0000-0002-7854-2139 Valerije Vrček author Michael Bühl author Protonated formylmetallocenes [M(C5H5)(C5H4-CHOH)]+ (M = Fe, Ru) and their isomers have been studied at the BP86 and B3LYP levels of density functional theory. Oxygen-protonated isomers are the most stable forms in each case, with a plethora of ring- or metal-protonated species at least ca. 14 and 10 kcal/mol higher in energy for M = Fe and Ru, respectively. The computed rotational barriers around the C−C bond connecting the cyclopentadienyl and protonated formyl moieties, ca. 18 kcal/mol, are indicative of substantial conjugation between these moieties. Some of the ring- and iron-protonated species are models for possible intermediates in Friedel–Crafts acylation of ferrocene, and the computations provide further evidence that exo attack is clearly favored over endo attack of the electrophile in this reaction. The structures of the most stable mono- and diprotonated formylferrocenes are corroborated by the good agreement between GIAO-B3LYP-computed and experimental NMR chemical shifts. American Chemical Society2008 eng Inorganic ChemistryOrganic ChemistryPhysical and Theoretical Chemistry Organometallics 0276-7333 1520-604110.1021/om700916f 273394-401 yes A. Šarić, V. Vrček, M. Bühl, Organometallics 27 (2008) 394–401. A. Šarić, V. Vrček, and M. Bühl, “Density functional study of protonated formylmetallocenes,” Organometallics, vol. 27, no. 3. American Chemical Society, pp. 394–401, 2008. Šarić, A., Vrček, V., & Bühl, M. (2008). Density functional study of protonated formylmetallocenes. Organometallics. American Chemical Society. <a href="https://doi.org/10.1021/om700916f">https://doi.org/10.1021/om700916f</a> Šarić, Anđela, et al. “Density Functional Study of Protonated Formylmetallocenes.” Organometallics, vol. 27, no. 3, American Chemical Society, 2008, pp. 394–401, doi:<a href="https://doi.org/10.1021/om700916f">10.1021/om700916f</a>. Šarić A, Vrček V, Bühl M. Density functional study of protonated formylmetallocenes. Organometallics. 2008;27(3):394-401. doi:<a href="https://doi.org/10.1021/om700916f">10.1021/om700916f</a> Šarić A, Vrček V, Bühl M. 2008. Density functional study of protonated formylmetallocenes. Organometallics. 27(3), 394–401. Šarić, Anđela, Valerije Vrček, and Michael Bühl. “Density Functional Study of Protonated Formylmetallocenes.” Organometallics. American Chemical Society, 2008. <a href="https://doi.org/10.1021/om700916f">https://doi.org/10.1021/om700916f</a>. 103922021-11-29T15:31:06Z2021-11-30T08:04:44Z