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• W4387527831 endingPage "136840" @default.
• W4387527831 startingPage "136840" @default.
• W4387527831 abstract "In this work, two new diiron(I) complexes of ferrole or ferracyclopentadiene type, [Fe2(CO)6{RC2(CH2)4C2R}] (R = H, 1; CH2CH3, 2) were synthesized by reacting the [Fe2(CO)9] with diynes (1,7-octadiyne and 3,9-dodecanediyne). The ferrole-type complexes were fully characterized, wherein the absolute structure of 2 was determined by single-crystal X-ray diffraction analysis. Interestingly, a rotational isomerization of the diiron(I) complexes (1 and 2) between the sawhorse conformer and the non-sawhorse conformer is verified, originated from the switch of CO coordination. Additionally, the sawhorse conformer with the terminal CO is dominant in solution due to the tricarbonyl iron units undergo a drastic geometrical turnstile rotation, whereas the non-sawhorse conformer with a semi-bridging CO is rigid in a solid state. Particularly, the isomerism of the diiron(I) complexes of ferrole type leads to a unique catalytic activity for hydroboration of aldehydes with pinacolborane (HBpin). Notably, twelve aldehydes (3a-3l) were exampled to be converted quantitatively into the corresponding organoboronates (4a-4l) mediated by complex 2 under mild conditions. Mechanistically, the 1H NMR and FTIR spectroscopic results proved that the ferrole-type complex 2 bound with the aldehyde to activate the carbonyl of the substrate rather than to cleave the H-B bond of pinacolborane. Collectively, a plausible mechanism for the catalytic hydroboration is proposed, with the rotational isomerization of the diiron(I) complexes involved in." @default.
• W4387527831 created "2023-10-12" @default.
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• W4387527831 date "2024-01-01" @default.
• W4387527831 modified "2023-10-16" @default.
• W4387527831 title "A rotational isomerization of diiron complexes of ferrole type involved in the catalytic hydroboration of aldehydes under mild conditions" @default.
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• W4387527831 doi "https://doi.org/10.1016/j.molstruc.2023.136840" @default.
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