Controlled ligand distortion and its consequences for structure, symmetry, conformation and spin-state preferences of iron(II) complexes.

Nicole Kroll,Marc Schoknecht,Martin Kaupp,Kolja Theilacker,Dirk Baabe,Gerald Hörner,Andreas Grohmann,Dennis Wiedemann

doi:10.1039/c5dt02502h

Abstract

The ligand-field strength in metal complexes of polydentate ligands depends critically on how the ligand backbone places the donor atoms in three-dimensional space. Distortions from regular coordination geometries are often observed. In this work, we study the isolated effect of ligand-sphere distortion by means of two structurally related pentadentate ligands of identical donor set, in the solid state (X-ray diffraction, (57)Fe-Mössbauer spectroscopy), in solution (NMR spectroscopy, UV/Vis spectroscopy, conductometry), and with quantum-chemical methods. Crystal structures of hexacoordinate iron(II) and nickel(II) complexes derived from the cyclic ligand L(1) (6-methyl-6-(pyridin-2-yl)-1,4-bis(pyridin-2-ylmethyl)-1,4-diazepane) and its open-chain congener L(2) (N(1),N(3),2-trimethyl-2-(pyridine-2-yl)-N(1),N(3)-bis(pyridine-2-ylmethyl) propane-1,3-diamine) reveal distinctly different donor set distortions reflecting the differences in ligand topology. Distortion from regular octahedral geometry is minor for complexes of ligand L(2), but becomes significant in the complexes of the cyclic ligand L(1), where trans elongation of Fe-N bonds cannot be compensated by the rigid ligand backbone. This provokes trigonal twisting of the ligand field. This distortion causes the metal ion in complexes of L(1) to experience a significantly weaker ligand field than in the complexes of L(2), which are more regular. The reduced ligand-field strength in complexes of L(1) translates into a marked preference for the electronic high-spin state, the emergence of conformational isomers, and massively enhanced lability with respect to ligand exchange and oxidation of the central ion. Accordingly, oxoiron(IV) species derived from L(1) and L(2) differ in their spectroscopic properties and their chemical reactivity.

Highlights

In vitro modelling of the biological function of a metal ion requires both an understanding of the factors governing its reactivity, and their control
Ligand synthesis Synthetic details for the 1,4-diazepane-based ligand L1 have been given in a previous publication.[29]
The open-chain ligand L2 was prepared from 2-methyl-2-( pyridine-2-yl)-propane-1,3diamine[32] in four steps with an overall yield of ca. 40%, (Scheme 2)

Summary

Introduction

We describe ligand-imposed distortion of the coordination environment as a powerful tool to tune the geometry, electronics and reactivity of a pair of iron(II) complexes. This approach decouples the metal centre under study from first-order ligand-field strength effects, as induced by donor set variation, either in terms of donor element (e.g., N vs O, vide supra) or in terms of hybridisation state within one class of donor atom (e.g., sp[2] N vs sp[3] N). Trigonal distortion of the coordination sphere, as a consequence of the angular constraint in L1, is clearly shown to reduce the ligand-field strength significantly, thereby favouring electronic high-spin states of the iron(II). Preliminary results indicate that ligand-imposed distortion causes the related oxoiron(IV) species to show distinctly different spectroscopic properties and reactivity

Results and discussion

Conclusions

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