[Cp′FeI]2 as convenient entry into iron-modified pincer complexes: bimetallic η6,κ1-POCOP-pincer iron iridium compounds

Walter, Marc D.; White, Peter S.

doi:10.1039/c1nj20399a

Cited by 51 publications

(60 citation statements)

References 71 publications

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“…The outcome of this experiment, however, is an unexpected facial coordination mode of the bimca ligand, to the best of our knowledge unprecedented for such a rigid ligand. Possible alternatives would have included an η 6 coordination to one of the benzene moieties or an η 5 coordination to the central pyrrole moiety of the carbazole backbone.…”

Section: Introductionsupporting

confidence: 74%

A Rigid CNC Pincer Ligand Acting as a Tripodal Cp Analogue

Jürgens

Kunz

2016

Eur J Inorg Chem

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Section: Introductionsupporting

confidence: 74%

A Rigid CNC Pincer Ligand Acting as a Tripodal Cp Analogue

Jürgens

Kunz

2016

Eur J Inorg Chem

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“…This interpretation is supported by Cp cent –Fe II distances above 190 pm for all structurally characterized high‐spin examples cited in this manuscript, whereas all such distances for low‐spin cyclopentadienyliron(II) complexes known to us are below 175 pm. Sterically bulky examples are hexa( tert ‐butyl)ferrocene or octaisopropylferrocene, both with 171 pm and slightly surpassed by decaphenylferrocene with 172 pm. A bulky half‐sandwich iron(II) complex with an 18‐valence‐electron low‐spin configuration and almost 173 pm 5 Cp cent –Fe distance will be presented below.…”

Section: Resultsmentioning

confidence: 99%

Iron(II) High‐Spin and Low‐Spin Complexes from Pentaisopropylcyclopentadienyliron(II) Bis(trimethylsilyl)amide

et al. 2017

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Two new complexes, [(C5Me5)FeBr(tmeda)] (tmeda = tetramethylethylenediamine) and [{C5(CHMe2)5}FeN(SiMe3)2], have been synthesized and characterized as high‐spin iron(II) complexes with typical distances between the iron atom and the center of gravity of the C5 ring (Fe–Cpcent) exceeding 190 pm and displaying paramagnetic behavior in solution. Both are analogues of known complexes, namely, the Jonas complex [(C5Me5)FeCl(tmeda)] and the Siemeling “pogo‐stick” complex [(C5Me5)FeN(SiMe3)2]. The silylamide [{C5(CHMe2)5}FeN(SiMe3)2] was treated with water to yield the bridged hydroxo dimer [{C5(CHMe2)5}Fe(µ‐OH)]2 with high‐spin iron(II) configuration. With 2,5‐dimethylpyrrole the azaferrocene derivative [{C5(CHMe2)5}Fe(NC4H2Me2‐2,5)] was obtained, and with diphenylphosphine a few crystals of the diphosphine hydride [{C5(CHMe2)5}FeH(HPPh2)2] as well as a sample of its dehydrogenative P–P coupling product [{C5(CHMe2)5}FeH(Ph2P–PPh2)]n (n = 1 or 2) have been obtained, which are both diamagnetic 18‐valence‐electron complexes. Two‐coordinated [{C5(CHMe2)5}FeN(SiMe3)2] features sizeable negative magnetic anisotropy and slow magnetic relaxation with an effective energy barrier for spin reversal of 113 cm–1 under an applied field of 3000 Oe.

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“…The suspicion of complex formation with nitrogen could be confirmed in the meantime 52,53 and will be the subject of a subsequent publication. 54 Initially we resorted, however, to diphenylacetylene as another triply bonded reaction partner in order to learn more about the reactivity of bulky alkylcyclopentadienyliron complexes such as [(C 5 H 2 t Bu 3 -1,2,4)Fe(μ-Br)] 2 (1), 55 64 Bis{tri(tert-butyl)cyclopentadienyliron(II) bromide} (1) and Its Reaction with Diphenylacetylene under Reducing Conditions. In a short communication the crystal structure of the bromo-bridged dimer 1 has been reported.…”

Section: Complexesmentioning

confidence: 99%

“…The high field shift of one tert-butyl group, whose resonance was found at 0.73 ppm, can be attributed to the anisotropy effect of the phenyl ring. 64 One mechanistic hypothesis assumes coordination of diphenylacetylene before the reduction takes place. There is, however, no visible change upon addition of diphenylacetylene to a solution of 1 in pentane.…”

Section: Complexesmentioning

confidence: 99%

Benzylidyne Bridges from Diphenylacetylene and a Methylidyne Bridge from Methylmagnesium Chloride

et al. 2015

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Preparation of the dimeric starting compound [(C5H2 tBu3-1,2,4)Fe(μ-Br)]2 (1) gave a small amount of its green sodium bromide adduct [(C5H2 tBu3-1,2,4)Fe(μ-Br)2Na(DME)2] (2). Reduction of 1 under argon in the presence of diphenylacetylene yielded dark red [(C5H2 tBu3-1,2,4)Fe(μ-CPh)]2 (3) containing two bridging benzylidyne ligands resulting from diphenylacetylene scission. The dicobalt methylidyne complex [{(C5HiPr4)Co}2(μ-CH)(μ-H)] (5) was obtained in high yield from the reaction of [(C5HiPr4)Co(μ-Cl)]2 (4) with two equivalents of methylmagnesium chloride. According to DFT calculations the dinuclear alkylidyne complexes 3 and 5 contain d6 metal centers, namely, iron(II) (3) and cobalt(III) (5). Whereas the benzylidyne ligands of the iron complex 3 display an empty orbital of p z character at the bridging carbon atom, the p z orbital of the methylidyne carbon in the dicobalt complex 5 is filled with a lone pair of electrons.

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[Cp′FeI]2 as convenient entry into iron-modified pincer complexes: bimetallic η6,κ1-POCOP-pincer iron iridium compounds

Cited by 51 publications

References 71 publications

A Rigid CNC Pincer Ligand Acting as a Tripodal Cp Analogue

A Rigid CNC Pincer Ligand Acting as a Tripodal Cp Analogue

Iron(II) High‐Spin and Low‐Spin Complexes from Pentaisopropylcyclopentadienyliron(II) Bis(trimethylsilyl)amide

Benzylidyne Bridges from Diphenylacetylene and a Methylidyne Bridge from Methylmagnesium Chloride

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