Comparing the reactivity of benzenedithiolate- versus alkyldithiolate- bridged Fe2(CO)6 complexes with competing ligands

Daniel Streich; Michael Karnahl; Yeni Astuti; Clyde W. Cady; Leif Hammarström; Reiner Lomoth; Sascha Ott

doi:10.1002/ejic.201001152

Comparing the reactivity of benzenedithiolate- versus alkyldithiolate- bridged Fe₂(CO)₆ complexes with competing ligands

Daniel Streich, Michael Karnahl, Yeni Astuti, Clyde W. Cady, Leif Hammarström, Reiner Lomoth, Sascha Ott

Uppsala University

Research output: Contribution to journal › Article › peer-review

27 Citations (Scopus)

Abstract

The reactivity of [(μ-X₂bdt)Fe₂(CO)₆] [(bdt)1, X₂bdt = 3,6-disubstituted bezenedithiolate; X = H, Cl] with ligands of different donor strengths is investigated and compared to that of [(μ-pdt)Fe₂(CO)₆] [(pdt)1, pdt = propyldithiolate] and [(μ-edt)Fe₂(CO)₆] [(edt)1, edt = ethyldithiolate]. Strong donor ligands (L = CN^-, PMe₃) when added to (bdt)1 lead to mononuclear [(bdt)Fe(L)₂(CO)₂], (bdt)6(L), in a disproportionation and fragmentation reaction, while simple ligand-substitution reactions occur on (edt)1 and (pdt)1 under identical conditions. In the presence of weaker ligands such as secondary amines or dmf, the alkyldithiolate-bridged complexes are unreactive, while (bdt)1 transforms to an O₂-sensitive, magnetically uncoupled species, potentially a mononuclear Fe^I complex coordinated by bdt and at least 2 CO ligands.

Original language	English
Pages (from-to)	1106-1111
Number of pages	6
Journal	European Journal of Inorganic Chemistry
Issue number	7
DOIs	https://doi.org/10.1002/ejic.201001152
Publication status	Published - Mar 2011

Keywords

Carbonyl ligands
Enzyme models
Hydrogenases
IR spectroscopy
S ligands

ASJC Scopus subject areas

Inorganic Chemistry

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10.1002/ejic.201001152

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Comparing the reactivity of benzenedithiolate- versus alkyldithiolate- bridged Fe₂(CO)₆ complexes with competing ligands. / Streich, Daniel; Karnahl, Michael; Astuti, Yeni; Cady, Clyde W.; Hammarström, Leif; Lomoth, Reiner; Ott, Sascha.

In: European Journal of Inorganic Chemistry, No. 7, 03.2011, p. 1106-1111.

Research output: Contribution to journal › Article › peer-review

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abstract = "The reactivity of [(μ-X2bdt)Fe2(CO)6] [(bdt)1, X2bdt = 3,6-disubstituted bezenedithiolate; X = H, Cl] with ligands of different donor strengths is investigated and compared to that of [(μ-pdt)Fe2(CO)6] [(pdt)1, pdt = propyldithiolate] and [(μ-edt)Fe2(CO)6] [(edt)1, edt = ethyldithiolate]. Strong donor ligands (L = CN-, PMe3) when added to (bdt)1 lead to mononuclear [(bdt)Fe(L)2(CO)2], (bdt)6(L), in a disproportionation and fragmentation reaction, while simple ligand-substitution reactions occur on (edt)1 and (pdt)1 under identical conditions. In the presence of weaker ligands such as secondary amines or dmf, the alkyldithiolate-bridged complexes are unreactive, while (bdt)1 transforms to an O2-sensitive, magnetically uncoupled species, potentially a mononuclear FeI complex coordinated by bdt and at least 2 CO ligands.",

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