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Issue 34, 2011
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The chemistry of hydridocarbonylferrates revisited: syntheses and structures of the new [H2Fe4(CO)12]2 and [HFe5(CO)14]3 anions, and the [Fe(DMF)4][Fe4(CO)1252-CO)(μ-H)]2 adduct containing an unprecedented isocarbonyl

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Abstract

The di-hydride di-anion [H2Fe4(CO)12]2 has been quantitatively obtained by protonation of the previously reported mono-hydride tri-anion [HFe4(CO)12]3 in DMSO and structurally characterised in its [NEt4]2[H2Fe4(CO)12] salt. It shows some subtle but yet significant differences in the stereochemistry of the ligands in comparison to the heavier Ru4 and Os4 congeners. The study of the reactivity of these [H4 − nFe4(CO)12]n (n = 2,3) species allowed the serendipitous isolation and structural characterization of the new pentanuclear [HFe5(CO)14]3mono-hydride tri-anion. Attempts to obtain the latter in better yields led to the discovery of intermolecular CO/H mutual exchange reactions and isolation and structural characterization of the [Fe(DMF)4][Fe4(CO)1252-CO)(μ-H)]2·0.5CH2Cl2 and [M+][Fe4(CO)1242-CO)(μ-H)] (M = K, Cs) adducts, the former containing an unprecedented isocarbonyl group. The isolation of new tetranuclear and, above all, pentanuclear hydridocarbonylferrates indicates that it is possible to further expand the chemistry of homoleptic Fe carbonyl species.

Graphical abstract: The chemistry of hydridocarbonylferrates revisited: syntheses and structures of the new [H2Fe4(CO)12]2− and [HFe5(CO)14]3− anions, and the [Fe(DMF)4][Fe4(CO)12(μ5-η2-CO)(μ-H)]2 adduct containing an unprecedented isocarbonyl

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Supplementary files

Article information


Submitted
13 Apr 2011
Accepted
09 Jun 2011
First published
27 Jul 2011

Dalton Trans., 2011,40, 8685-8694
Article type
Paper

The chemistry of hydridocarbonylferrates revisited: syntheses and structures of the new [H2Fe4(CO)12]2 and [HFe5(CO)14]3 anions, and the [Fe(DMF)4][Fe4(CO)1252-CO)(μ-H)]2 adduct containing an unprecedented isocarbonyl

C. Femoni, M. C. Iapalucci, G. Longoni and S. Zacchini, Dalton Trans., 2011, 40, 8685
DOI: 10.1039/C1DT10648A

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