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Issue 25, 2014
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Deprotonation/protonation-driven change of the σ-donor ability of a sulfur atom in iron(II) complexes with a thioamide SNS pincer type ligand

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Abstract

A new iron complex with a thioamide SNS pincer type ligand, [FeBr23-H2LDPM)] (κ3-H2LDPM = 2,6-bis(N-2,6-bis(diphenylmethyl)-4-isopropylphenylthioamide)pyridine), was synthesized. This complex reacts with NaH in THF to yield a unique Fe(II) complex with two THF molecules, [Fe(THF)23-LDPM)] (κ3-LDPM = 2,6-bis(N-2,6-bis(diphenylmethyl)-4-isopropylphenyliminothiolate)pyridine). The THF molecules of [Fe(THF)23-LDPM)] can be substituted with CO and CN-xylyl to give [Fe(CO)33-LDPM)] and [Fe(CN-xylyl)33-LDPM)], respectively. The complex [Fe(CN-xylyl)33-LDPM)] reacts with HBF4 to produce [Fe(CN-xylyl)33-H2LDPM)]2+ with protonated thioamide units. The differences of the IR spectra before and after protonation indicate that the major binding mode of CN-xylyl to iron(II) changes from π-back donation from metal to isocyanide to σ-donation from isocyanide to iron(II). This indicates that the σ-donor ability of the thioamide sulfur atom is tuned by deprotonation/protonation of thioamide.

Graphical abstract: Deprotonation/protonation-driven change of the σ-donor ability of a sulfur atom in iron(ii) complexes with a thioamide SNS pincer type ligand

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Publication details

The article was received on 19 Feb 2014, accepted on 23 Apr 2014 and first published on 29 Apr 2014


Article type: Paper
DOI: 10.1039/C4DT00524D
Citation: Dalton Trans., 2014,43, 9732-9739
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    Deprotonation/protonation-driven change of the σ-donor ability of a sulfur atom in iron(II) complexes with a thioamide SNS pincer type ligand

    T. Suzuki, Y. Kajita and H. Masuda, Dalton Trans., 2014, 43, 9732
    DOI: 10.1039/C4DT00524D

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