Homoleptic mono-, di-, and tetra-iron complexes featuring phosphido ligands: a synthetic, structural, and spectroscopic study

Kinga Kaniewska-Laskowska; Łukasz Ponikiewski; Natalia Szynkiewicz; Bartłomiej Cieślik; Jerzy Pikies; J. Krzystek; Alina Dragulescu-Andrasi; Sebastian Stoian; Rafał Grubba

doi:10.1039/d0dt01503b

Homoleptic mono-, di-, and tetra-iron complexes featuring phosphido ligands: a synthetic, structural, and spectroscopic study

Abstract

We report the first series of homoleptic phosphido iron complexes synthesized by treating either the β-diketiminato complex [(Dippnacnac)FeCl2Li(dme)2] (Dippnacnac = HC[(CMe)N(C6H3-2,6-iPr2)]2) or [FeBr2(thf )2] with an excess of phosphides R2PLi (R = tBu, tBuPh, Cy, iPr). Reaction outcomes depend strongly on the bulkiness of the phosphido ligands. The use of tBu2PLi precursor led to an anionic diiron complex 1 encompassing a planar Fe2P2 core with two bridging and two terminal phosphido ligands. An analogous reaction employing less sterically demanding phosphides, tBuPhPLi and Cy2PLi yielded diiron anionic complexes 2 and 3, respectively, featuring a short Fe–Fe interaction supported by three bridging phosphido groups and one additional terminal R2P− ligand at each iron center. Further tuning of the P-substrates bulkiness gave a neutral phosphido complex 4 possessing a tetrahedral Fe4 cluster core held together by six bridging iPr2P moieties. Moreover, we also describe the first homoleptic phosphanylphosphido iron complex 5, which features an iron center with low coordination provided by three tBu2P-P(SiMe3)− ligands. The structures of compounds 1–5 were determined by single-crystal X-ray diffraction and 1–3 by 1H NMR spectroscopy. Moreover, the electronic structures of 1–3 were interrogated using zero-field Mössbauer spectroscopy and DFT methods.

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Authors (9)

Kinga Kaniewska-Laskowska (formerly: Kinga Kaniewska) dr inż.
Łukasz Ponikiewski dr hab. inż.
Natalia Szynkiewicz mgr inż.
Bartłomiej Cieślik dr inż.
Jerzy Pikies prof. dr hab. inż.
J. Krzystek
Alina Dragulescu-Andrasi
Sebastian Stoian
Rafał Grubba dr hab. inż.

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License: Copyright (2020 The Royal Society of Chemistry)

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artykuły w czasopismach

Published in:

DALTON TRANSACTIONS no. 49, pages 10091 - 10103,
ISSN: 1477-9226

Language:

English

Publication year:

2020

Bibliographic description:

Kaniewska K., Ponikiewski Ł., Szynkiewicz N., Cieślik B., Pikies J., Krzystek J., Dragulescu-Andrasi A., Stoian S., Grubba R.: Homoleptic mono-, di-, and tetra-iron complexes featuring phosphido ligands: a synthetic, structural, and spectroscopic study// DALTON TRANSACTIONS -Vol. 49,iss. 29 (2020), s.10091-10103

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