Unexpected assembly of a novel triply bridged diiron(II) core by a bidentate Schiff base ligand |
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Authors: | Aubrey L. Smith Lawrence Que Jr. Ulrich Bierbach |
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Affiliation: | a Department of Chemistry, Wake Forest University, Winston-Salem, NC 27109, USA b Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, MN 55455, USA |
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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 (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. |
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Keywords: | Schiff base Diiron(II) complex Ferromagnetic coupling Crystal structure EPR spectroscopy |
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