Unexpected assembly of a novel triply bridged diiron(II) core by a bidentate Schiff base ligand

Aubrey L. Smith; Cynthia S. Day; Lawrence Que; Yuming Zhou; Ulrich Bierbach

doi:10.1016/j.ica.2007.01.001

Unexpected assembly of a novel triply bridged diiron(II) core by a bidentate Schiff base ligand

Aubrey L. Smith, Cynthia S. Day, Lawrence Que, Yuming Zhou, Ulrich Bierbach

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

5 Scopus citations

Abstract

The unusual dinucleating properties of a simple bidentate Schiff base (LH, 1) in the presence of weakly coordinating methanol solvent lead to the self-assembly of [Fe₂^II (L_b)₂ (L_t)₂ (μ - MeOH)] (2) (b and t refer to bridging and terminally bound ligands, respectively). Complex 2 is the first diiron(II) species in which the two metal centers are triply bridged by single atoms in an asymmetric fashion, involving both μ-O^Ph and μ-OH^Me bridges. This binding mode produces an Fe⋯Fe distance of 3.139(1) Å. Dinucleation appears to be driven by a combination of ligand deficiency and solvent-mediated chemistry reminiscent of host-guest interactions. The presence of a μ-MeOH ligand is unprecedented in iron chemistry. Parallel-mode EPR spectra of complex 2 recorded at 4 K show an intense negative signal at g_∥ ≈ 16, suggesting the dimeric form exists in solution.

Original language	English (US)
Pages (from-to)	2824-2828
Number of pages	5
Journal	Inorganica Chimica Acta
Volume	360
Issue number	8
DOIs	https://doi.org/10.1016/j.ica.2007.01.001
State	Published - May 30 2007

Bibliographical note

Funding Information:
We thank Dr. M.W. Wright (WFU) for assistance with the NMR data acquisitions. This research was supported by the Science Research Fund of WFU (U.B.) and the NIH (GM-38767 to L.Q.).

Keywords

Crystal structure
Diiron(II) complex
EPR spectroscopy
Ferromagnetic coupling
Schiff base

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title = "Unexpected assembly of a novel triply bridged diiron(II) core by a bidentate Schiff base ligand",

abstract = "The unusual dinucleating properties of a simple bidentate Schiff base (LH, 1) in the presence of weakly coordinating methanol solvent lead to the self-assembly of [Fe2II (Lb)2 (Lt)2 (μ - MeOH)] (2) (b and t refer to bridging and terminally bound ligands, respectively). Complex 2 is the first diiron(II) species in which the two metal centers are triply bridged by single atoms in an asymmetric fashion, involving both μ-OPh and μ-OHMe bridges. This binding mode produces an Fe⋯Fe distance of 3.139(1) {\AA}. Dinucleation appears to be driven by a combination of ligand deficiency and solvent-mediated chemistry reminiscent of host-guest interactions. The presence of a μ-MeOH ligand is unprecedented in iron chemistry. Parallel-mode EPR spectra of complex 2 recorded at 4 K show an intense negative signal at g∥ ≈ 16, suggesting the dimeric form exists in solution.",

keywords = "Crystal structure, Diiron(II) complex, EPR spectroscopy, Ferromagnetic coupling, Schiff base",

author = "Smith, {Aubrey L.} and Day, {Cynthia S.} and Lawrence Que and Yuming Zhou and Ulrich Bierbach",

note = "Funding Information: We thank Dr. M.W. Wright (WFU) for assistance with the NMR data acquisitions. This research was supported by the Science Research Fund of WFU (U.B.) and the NIH (GM-38767 to L.Q.). ",

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T1 - Unexpected assembly of a novel triply bridged diiron(II) core by a bidentate Schiff base ligand

AU - Smith, Aubrey L.

AU - Day, Cynthia S.

AU - Que, Lawrence

AU - Zhou, Yuming

AU - Bierbach, Ulrich

N1 - Funding Information: We thank Dr. M.W. Wright (WFU) for assistance with the NMR data acquisitions. This research was supported by the Science Research Fund of WFU (U.B.) and the NIH (GM-38767 to L.Q.).

PY - 2007/5/30

Y1 - 2007/5/30

N2 - The unusual dinucleating properties of a simple bidentate Schiff base (LH, 1) in the presence of weakly coordinating methanol solvent lead to the self-assembly of [Fe2II (Lb)2 (Lt)2 (μ - MeOH)] (2) (b and t refer to bridging and terminally bound ligands, respectively). Complex 2 is the first diiron(II) species in which the two metal centers are triply bridged by single atoms in an asymmetric fashion, involving both μ-OPh and μ-OHMe bridges. This binding mode produces an Fe⋯Fe distance of 3.139(1) Å. Dinucleation appears to be driven by a combination of ligand deficiency and solvent-mediated chemistry reminiscent of host-guest interactions. The presence of a μ-MeOH ligand is unprecedented in iron chemistry. Parallel-mode EPR spectra of complex 2 recorded at 4 K show an intense negative signal at g∥ ≈ 16, suggesting the dimeric form exists in solution.

AB - The unusual dinucleating properties of a simple bidentate Schiff base (LH, 1) in the presence of weakly coordinating methanol solvent lead to the self-assembly of [Fe2II (Lb)2 (Lt)2 (μ - MeOH)] (2) (b and t refer to bridging and terminally bound ligands, respectively). Complex 2 is the first diiron(II) species in which the two metal centers are triply bridged by single atoms in an asymmetric fashion, involving both μ-OPh and μ-OHMe bridges. This binding mode produces an Fe⋯Fe distance of 3.139(1) Å. Dinucleation appears to be driven by a combination of ligand deficiency and solvent-mediated chemistry reminiscent of host-guest interactions. The presence of a μ-MeOH ligand is unprecedented in iron chemistry. Parallel-mode EPR spectra of complex 2 recorded at 4 K show an intense negative signal at g∥ ≈ 16, suggesting the dimeric form exists in solution.

KW - Crystal structure

KW - Diiron(II) complex

KW - EPR spectroscopy

KW - Ferromagnetic coupling

KW - Schiff base

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ER -

Unexpected assembly of a novel triply bridged diiron(II) core by a bidentate Schiff base ligand

Abstract

Bibliographical note

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