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Synthesis, Structures, and Electronic Properties of [8Fe-7S] Cluster Complexes Modeling the Nitrogenase P-Cluster

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Department of Chemistry, Graduate School of Science and Research Center for Materials Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan, Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japan, and Graduate School of Science and Engineering, Tokyo Metropolitan University, Minami-ohsawa, Hachioji, Tokyo 192-0397, Japan
[email protected]
†Nagoya University.
¶Kyoto University.
‡Tokyo Metropolitan University.
Cite this: J. Am. Chem. Soc. 2009, 131, 36, 13168–13178
Publication Date (Web):August 20, 2009
https://doi.org/10.1021/ja9055036
Copyright © 2009 American Chemical Society
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Abstract

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High-yield synthesis of the iron−sulfur cluster [{N(SiMe3)2}{SC(NMe2)2}Fe4S3]2(μ6-S) {μ-N(SiMe3)2}2 (1), which reproduces the [8Fe-7S] core structure of the nitrogenase PN-cluster, has been achieved via two pathways: (1) Fe{N(SiMe3)2}2 + HSTip (Tip = 2,4,6-iPr3C6H2) + tetramethylthiourea (SC(NMe2)2) + elemental sulfur (S8); and (2) Fe3{N(SiMe3)2}2(μ-STip)4 (2) + HSTip + SC(NMe2)2 + S8. The thiourea and terminal amide ligands of 1 were found to be replaceable by thiolate ligands upon treatment with thiolate anions and thiols at −40 °C, respectively, and a series of [8Fe-7S] clusters bearing two to four thiolate ligands have been synthesized and their structures were determined by X-ray analysis. The structures of these model [8Fe-7S] clusters all closely resemble that of the reduced form of P-cluster (PN) having 8Fe(II) centers, while their 6Fe(II)−2Fe(III) oxidation states correspond to the oxidized form of P-cluster (POX). The cyclic voltammograms of the [8Fe-7S] clusters reveal two quasi-reversible one-electron reduction processes, leading to the 8Fe(II) state that is the same as the PN-cluster, and the synthetic models demonstrate the redox behavior between the two major oxidation states of the native P-cluster. Replacement of the SC(NMe2)2 ligands in 1 with thiolate anions led to more negative reduction potentials, while a slight positive shift occurred upon replacement of the terminal amide ligands with thiolates. The clusters 1, (NEt4)2[{N(SiMe3)2}(SC6H4-4-Me)Fe4S3]2(μ6-S){μ-N(SiMe3)2}2 (3a), and [(SBtp){SC(NMe2)2}Fe4S3]2(μ6-S){μ-N(SiMe3)2}2 (5; Btp = 2,6-(SiMe3)2C6H3) are EPR silent at 4−100 K, and their temperature-dependent magnetic moments indicate a singlet ground state with antiferromagnetic couplings among the iron centers. The 57Fe Mössbauer spectra of these clusters are consistent with the 6Fe(II)−2Fe(III) oxidation state, each exhibiting two doublets with an intensity ratio of ca. 1:3, which are assignable to Fe(III) and Fe(II), respectively. Comparison of the quadrupole splittings for 1, 3a, and 5 has led to the conclusion that two Fe(III) sites of the clusters are the peripheral iron atoms.

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Details of X-ray crystallographic studies of 1, 3a−e, 4, 5, 6, 7b, and (PPh4)2[Fe4S4(SPh)4] (PDF), and an X-ray crystallographic information file (CIF). This material is available free of charge via the Internet at http://pubs.acs.org.

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