Quantitative Geometric Descriptions of the Belt Iron Atoms of the Iron-Molybdenum Cofactor of Nitrogenase and Synthetic Iron(II) Model Complexes
2007
Six of the seven iron atoms in the iron−molybdenum cofactor of nitrogenase display an unusual geometry, which is distorted from the tetrahedral geometry that is most common in iron−sulfur clusters. This distortion pulls the iron along one C3 axis of the tetrahedron toward a trigonal pyramid. The trigonal pyramidal coordination geometry is rare in four-coordinate transition metal complexes. In order to document this geometry in a systematic fashion in iron(II) chemistry, we have synthesized a range of four-coordinate iron(II) complexes that vary from tetrahedral to trigonal pyramidal. Continuous shape measures are used for a quantitative comparison of the stereochemistry of the Fe atoms in the iron−molybdenum cofactor with those of the presently and previously reported model complexes, as well as with those in polynuclear iron−sulfur compounds. This understanding of the iron coordination geometry is expected to assist in the design of synthetic analogues for intermediates in the nitrogenase catalytic cycle.
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