Acridine-based copper(<scp>i</scp>) PNP pincer complexes: catalysts for alkyne hydroboration and borylation of aryl halides

Olding, Angus; Lucas, Nigel. T.; Ho, Curtis C.; Bissember, Alex C.

doi:10.1039/d3dt04269c

Dalton Trans.

2024

DOI: 10.1039/d3dt04269c

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Acridine-based copper(i) PNP pincer complexes: catalysts for alkyne hydroboration and borylation of aryl halides

Angus Olding,

Nigel. T. Lucas,

Curtis C. Ho

et al.

Abstract: PNP pincers represent some of the most well-studied ligand systems in coordination chemistry owing to their high thermal and chemical stability, and the predictable metal coordination geometries of associated metal...

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Iron Complexes of 4,5-Bis(diorganophosphinomethyl)acridine Ligands

Roca Jungfer,

Rominger,

Oeser

et al. 2024

Inorg. Chem.

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The search for an iron analog of the established ruthenium-based catalysts containing methylene-extended 4,5bis(diorganophosphinomethyl)acridine ligands, [FeHCl(CO)-(L R )], resulted in the discovery of a bidentate coordination mode of these usually tridentate pincer ligands toward iron. The acridines nitrogen atom does not coordinate to iron, leading to the formation of iron diphos-type complexes with unusually large cis bite angles of up to 124°as well as trans bite angles around 155°. The iron-containing complexeshave been isolated in crystalline form and characterized by spectroscopic methods and mass spectrometry. Their structures were verified unambiguously through X-ray diffraction. The stability of the iron(II) complexes decreased in the order Cy > Ph > i Pr and Cl > Br > I, although all iron(II) complexes were found to be relatively stable enough for short-term handling in air in the solid state. Notably, no iron(0) complex of the phenyl derivative could be isolated. The iron(0) complex [Fe(CO) 3 (κ 2 -L Cy )] was found to be significantly more stable toward hydrolysis and oxygen compared to [Fe(CO) 3 (κ 2 -L iPr )] and can be stored in air for months without significant decomposition in the solid state, while [Fe(CO) 3 (κ 2 -L iPr )] decomposes in air within seconds. The decomposition products [FeI 2 (κ 2 -O 2 L Cy )], [{Fe(CO) 3 (κ 2 -HL R )} 2 ] (R = i Pr, Cy) and [FeCl 2 (CO) 2 (κ 1 -L Cy )(κ 1 -OL Cy )] were identified and characterized crystallographically. The iron(0) complex [Fe(CO) 3 (κ 2 -L Cy )] is oxidized by [Fe(Cp) 2 ](BPh 4 ) to give the paramagnetic, low-spin iron(I) cation [Fe(CO) 3 (κ 2 -L Cy )] + . The electron paramagnetic resonance spectrum of the highly sensitive cation as well as density functional theory calculations suggest a partial delocalization of the unpaired electron over the three carbonyl ligands and the acridines aromatic ring system. The catalytic activity and photophysical properties of the complexes have been preliminarily investigated.

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Iron Complexes of 4,5-Bis(diorganophosphinomethyl)acridine Ligands

Roca Jungfer,

Rominger,

Oeser

et al. 2024

Inorg. Chem.

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show abstract

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Acridine-based copper(i) PNP pincer complexes: catalysts for alkyne hydroboration and borylation of aryl halides

Abstract: PNP pincers represent some of the most well-studied ligand systems in coordination chemistry owing to their high thermal and chemical stability, and the predictable metal coordination geometries of associated metal...

Cited by 1 publication

References 51 publications

Iron Complexes of 4,5-Bis(diorganophosphinomethyl)acridine Ligands

Iron Complexes of 4,5-Bis(diorganophosphinomethyl)acridine Ligands

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