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Microwave-assisted synthesis of cyclopentadienone iron tricarbonyl complexes: molecular structures of [{eta(4)-C4R2C(O)C4H8}Fe(CO)(3)] (R = Ph, 2,4-F2C6H3, 4-MeOC6H4) and attempts to prepare Fe(II) hydroxycyclopentadienyl-hydride complexes

Richard, CJ; Macmillan, D; Hogarth, G; (2018) Microwave-assisted synthesis of cyclopentadienone iron tricarbonyl complexes: molecular structures of [{eta(4)-C4R2C(O)C4H8}Fe(CO)(3)] (R = Ph, 2,4-F2C6H3, 4-MeOC6H4) and attempts to prepare Fe(II) hydroxycyclopentadienyl-hydride complexes. Transition Metal Chemistry , 43 (5) pp. 421-430. 10.1007/s11243-018-0229-1. Green open access

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Abstract

Microwave irradiation of 1,6-diynes, RC≡C(CH2)4C≡CR, with Fe(CO)5 in dimethylether leads to the facile and clean formation of cyclopentadienone complexes [{η4-C4R2C(O)C4H8}Fe(CO)3] in good yields resulting from a [2 + 2 + 1] cycloaddition. The molecular structures of three examples (R = Ph, 2,4-F2C6H3, 4-MeOC6H4) have been obtained. The addition of HBF4 leads to the clean and reversible formation of cationic hydroxycyclopentadienyl complexes [{η5-C4R2C(OH)C4H8}Fe(CO)3][BF4]. Sequential addition of hydroxide and acid has also been carried out in an attempt to prepare hydroxycyclopentadienyl–hydride complexes. These were largely unsuccessful but in one case a Shvo-type complex with a bridging hydride was detected by 1H NMR spectroscopy. Reasons for the differing behaviour of [{η4-C4(SiMe3)2C(O)C4H8}Fe(CO)3] and the related aryl-functionalised derivatives are considered.

Type: Article
Title: Microwave-assisted synthesis of cyclopentadienone iron tricarbonyl complexes: molecular structures of [{eta(4)-C4R2C(O)C4H8}Fe(CO)(3)] (R = Ph, 2,4-F2C6H3, 4-MeOC6H4) and attempts to prepare Fe(II) hydroxycyclopentadienyl-hydride complexes
Open access status: An open access version is available from UCL Discovery
DOI: 10.1007/s11243-018-0229-1
Publisher version: https://doi.org/10.1007/s11243-018-0229-1
Language: English
Additional information: This article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made.
Keywords: Science & Technology, Physical Sciences, Chemistry, Inorganic & Nuclear, Chemistry, OPPENAUER-TYPE OXIDATION, LIGAND-EXCHANGE REACTION, RUTHENIUM COMPLEXES, TRANSFER HYDROGENATION, ASYMMETRIC CATALYSIS, REDUCTIVE AMINATION, CARBONYL-COMPLEXES, ORGANIC-SYNTHESIS, DIENE COMPLEXES, KETONES
UCL classification: UCL
UCL > Provost and Vice Provost Offices
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry
URI: https://discovery-pp.ucl.ac.uk/id/eprint/10054671
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