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An iron(ii) hydride complex of a ligand with two adjacent ?-diketiminate binding sites and its reactivity.

ABSTRACT: After lithiation of PYR-H2 (PYR = [(NC(Me)C(H)C(Me)NC6H3(iPr)2)2(C5H3N)](2-)) - the precursor of an expanded ?-diketiminato ligand system with two binding pockets - with KN(TMS)2 the reaction of the resulting potassium salt with FeBr2 led to a dinuclear iron(ii) bromide complex [(PYR)Fe(?-Br)2Fe] (1). Through treatment with KHBEt3 the bromide ligands could be replaced by hydrides to yield [PYR)Fe2(?-H)2] (2), a distorted analogue of known ?-diketiminato iron hydride complexes, as evidenced by NMR, Mößbauer and X-ray absorption spectroscopy, as well as by its reactivity: for instance, 2 reacts with the proton source lutidinium triflate via protonation of the hydride ligands to form an iron(ii) product [(PYR)Fe2(OTf)2] (4), while CO2 inserts into the Fe-H bonds generating the formate complex [(PYR)Fe2(?-HCOO)2] (5); in the presence of traces of water partial hydrolysis occurs so that [(PYR)Fe2(?-OH)(?-HCOO)] (6) is isolated. Altogether, the iron(ii) chemistry supported by the PYR(2-) ligand is distinctly different from the one of nickel(ii), where both, the arrangement of the two binding pockets and the additional pyridyl donor led to diverging features as compared with the corresponding system based on the parent ?-diketiminato ligand.

SUBMITTER: Gehring H

PROVIDER: S-EPMC5536248 | biostudies-literature | 2016 Feb

REPOSITORIES: biostudies-literature

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An iron(ii) hydride complex of a ligand with two adjacent β-diketiminate binding sites and its reactivity.

Gehring Henrike H Metzinger Ramona R Braun Beatrice B Herwig Christian C Harder Sjoerd S Ray Kallol K Limberg Christian C

Dalton transactions (Cambridge, England : 2003) 20160113 7

After lithiation of PYR-H2 (PYR = [(NC(Me)C(H)C(Me)NC6H3(iPr)2)2(C5H3N)](2-)) - the precursor of an expanded β-diketiminato ligand system with two binding pockets - with KN(TMS)2 the reaction of the resulting potassium salt with FeBr2 led to a dinuclear iron(ii) bromide complex [(PYR)Fe(μ-Br)2Fe] (1). Through treatment with KHBEt3 the bromide ligands could be replaced by hydrides to yield [PYR)Fe2(μ-H)2] (2), a distorted analogue of known β-diketiminato iron hydride complexes, as evidenced by NM ...[more]

PMID: 26757878

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Project description:The iron(II) semiquinonate character within the iron(III) catecholate species has been proposed by numerous studies to account for the O2 reactivity of intradiol catechol dioxygenases, but a well-characterized iron(II) semiquinonate species that exhibits intradiol cleaving reactivity has not yet been reported. In this study, a detailed electronic structure description of the first iron(II) o-semiquinonate complex, [PhTttBu]Fe(phenSQ) [PhTttBu = phenyltris(tert-butylthiomethyl)borate; phenSQ = 9,10-phenanthrenesemiquinonate; Wang et al. Chem. Commun. 2014, 50, 5871-5873], was generated through a combination of electronic and Mössbauer spectroscopies, SQUID magnetometry, and density functional theory (DFT) calculations. [PhTttBu]Fe(phenSQ) reacts with O2 to generate an intradiol cleavage product, diphenic anhydride, in 16% yield. To assess the dependence of the intradiol reactivity on the identity of the metal ion, the nickel analogue, [PhTttBu]Ni(phenSQ), and its derivative, [PhTttBu]Ni(3,5-DBSQ) (3,5-DBSQ = 3,5-di-tert-butyl-1,2-semiquinonate), were prepared and characterized by X-ray crystallography, mass spectrometry, 1H NMR and electronic spectroscopies, and SQUID magnetometry. DFT calculations, evaluated on the basis of the experimental data, support the electronic structure descriptions of [PhTttBu]Ni(phenSQ) and [PhTttBu]Ni(3,5-DBSQ) as high-spin nickel(II) complexes with antiferromagnetically coupled semiquinonate ligands. Unlike its iron counterpart, [PhTttBu]Ni(phenSQ) decomposes slowly in an O2 atmosphere to generate 14% phenanthrenequinone with a negligible amount of diphenic anhydride. [PhTttBu]Ni(3,5-DBSQ) does not react with O2. This dramatic effect of the metal-ion identity supports the hypothesis that a metal(III) alkylperoxo species serves as an intermediate in the intradiol cleaving reactions. The redox properties of all three complexes were probed using cyclic voltammetry and differential pulse voltammetry, which indicate an inner-sphere electron-transfer mechanism for the formation of phenanthrenequinone. The lack of O2 reactivity of [PhTttBu]Ni(3,5-DBSQ) can be rationalized by the high redox potential of the metal-ligated 3,5-DBSQ/3,5-DBQ couple.

Dataset Information

An iron(ii) hydride complex of a ligand with two adjacent ?-diketiminate binding sites and its reactivity.

Publications

An iron(ii) hydride complex of a ligand with two adjacent β-diketiminate binding sites and its reactivity.

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