Synthesis of the P-Cluster Inorganic Core of Nitrogenases

Ohki, Yasuhiro; Sunada, Yusuke; Honda, Masahiro; Katada, Motomi; Tatsumi, Kazuyuki

doi:10.1021/ja029383m

Cited by 107 publications

(67 citation statements)

References 27 publications

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“…An amide nitrogen atom (N1) and a sulfur atom of ½1 − interact weakly with a NaðTHFÞ 2 unit, and the Na-N1 and Na-S distances are 2.528(2) Å and 3.1992 (11) Reactions of 1 and ½1 − with HSDmp (Dmp¼2,6-ðmesitylÞ 2 C 6 H 3 ). The amide nitrogen of NðSiMe 3 Þ 2 bound to iron is a Brϕnstead base, and we have utilized this property to synthesize various iron-sulfide clusters (22)(23)(24)(25). Here, we describe the reactions of clusters 1 and ½1 − with the bulky thiol HSDmp ðDmp ¼ 2;6-ðmesitylÞ 2 C 6 H 3 Þ (26).…”

Section: Resultsmentioning

confidence: 99%

Synthetic analogues of [Fe ₄ S ₄ (Cys) ₃ (His)] in hydrogenases and [Fe ₄ S ₄ (Cys) ₄ ] in HiPIP derived from all-ferric [Fe ₄ S ₄ {N(SiMe ₃ ) ₂ }
Ohki
¹
,
Tanifuji
²
,
Yamada
³

et al. 2011
Proc. Natl. Acad. Sci. U.S.A.
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The all-ferric ½Fe 4 S 4 4þ cluster ½Fe 4 S 4 fNðSiMe 3 Þ 2 g 4 1 and its oneelectron reduced form ½1 − serve as convenient precursors for the synthesis of 3∶1-site differentiated ½Fe 4 S 4 clusters and highpotential iron-sulfur protein (HiPIP) model clusters. The reaction of 1 with four equivalents (equiv) of the bulky thiol HSDmp (Dmp¼ 2,6-ðmesitylÞ 2 C 6 H 3 , mesityl ¼2,4,6-Me 3 C 6 H 2 ) followed by treatment with tetrahydrofuran (THF) resulted in the isolation of ½Fe 4 S 4 ðSDmpÞ 3 ðTHFÞ 3 2. Cluster 2 contains an octahedral iron atom with three THF ligands, and its FeðSÞ 3 ðOÞ 3 coordination environment is relevant to that in the active site of substrate-bound aconitase. An analogous reaction of ½1 − with four equiv of HSDmp gave ½Fe 4 S 4 ðSDmpÞ 4 − 3, which models the oxidized form of HiPIP. The THF ligands in 2 can be replaced by tetramethyl-imidazole (Me 4 Im) to give ½Fe 4 S 4 ðSDmpÞ 3 ðMe 4 ImÞ 4 modeling the ½Fe 4 S 4 ðCysÞ 3 ðHisÞ cluster in hydrogenases, and its one-electron reduced form ½4 − was synthesized from the reaction of 3 with Me 4 Im. The reversible redox couple between 3 and ½3 − was observed at E 1∕2 ¼−820 mV vs. Ag∕Ag þ , and the corresponding reversible couple for 4 and ½4 − is positively shifted by þ440 mV. The cyclic voltammogram of 3 also exhibited a reversible oxidation couple, which indicates generation of the all-ferric ½Fe 4 S 4 4þ cluster, ½Fe 4 S 4 ðSDmpÞ 4 .Fe4S4 cluster | thiolates C uboidal ½Fe 4 S 4 clusters are ubiquitous metal-centers in proteins, expediting electron transfer and enzymatic reactions. These ½Fe 4 S 4 cores are usually bound to four cysteinyl thiolates (Cys) as found in the high-potential iron-sulfur proteins (HiPIP) and widely distributed ferredoxins (Fd). Some ½Fe 4 S 4 clusters carrying an N-or O-donor ligand and three Cys ligands are also known, for example the ½Fe 4 S 4 ðCysÞ 3 ðHisÞ cluster (His ¼ histidinyl imidazole) in [NiFe] and [FeFe] hydrogenases ( Fig. 1) (1-6), and the ½Fe 4 S 4 ðCysÞ 3 ðO-donorÞ cluster in aconitase (7-9) and protochlorophyllide reductase (10). All of these ½Fe 4 S 4 clusters are present in three oxidation states, ½Fe 4 S 4 3þ (HiPIP ox ), ½Fe 4 S 4 2þ (HiPIP red ∕Fd ox ), and ½Fe 4 S 4 þ (Fd red ), while the ½Fe 4 S 4 0 state has been suggested for the cluster in the Fe-protein of nitrogenase (11,12). To date, no ½Fe 4 S 4 4þ cluster has been found in proteins.

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Section: Resultsmentioning

confidence: 99%

Synthetic analogues of [Fe ₄ S ₄ (Cys) ₃ (His)] in hydrogenases and [Fe ₄ S ₄ (Cys) ₄ ] in HiPIP derived from all-ferric [Fe ₄ S ₄ {N(SiMe ₃ ) ₂ }
Ohki
¹
,
Tanifuji
²
,
Yamada
³

et al. 2011
Proc. Natl. Acad. Sci. U.S.A.
Self Cite
43
1
29
0
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“…Such a reaction mechanism has been well established in synthetic chemistry (38) and successfully realized by the recent synthesis of P-cluster topologs (19,40,41,57,59). The biological evidence in this regard was supplied by the characterization of a MoFe protein isolated from the nifH deletion background of A. vinelandii (designated the ⌬nifH MoFe protein).…”

Section: Reductive Coupling Of Paired [Fe 4 S 4 ] Subclusters Into a mentioning

confidence: 96%

Biosynthesis of the Metalloclusters of Molybdenum Nitrogenase

Ribbe

2011

Microbiol Mol Biol Rev

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SUMMARY Nitrogenase catalyzes a key step in the global nitrogen cycle, the nucleotide-dependent reduction of atmospheric dinitrogen to bioavailable ammonia. There is a substantial amount of interest in elucidating the biosynthetic mechanisms of the FeMoco and the P-cluster of nitrogenase, because these clusters are not only biologically important but also chemically unprecedented. In this review, we summarize the recent advances in this research area, with an emphasis on our work that aims at providing structural and spectroscopic insights into the assembly of these complex metalloclusters.

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“…In this respect, synthesis of neutral MoFe 3 S 4 clusters is attractive, because they may be dissolved in non-polar solvents, and assemblage of metal sulfide clusters in non-polar solvents would expand the scope of cluster synthesis. In fact, we were successful in isolating a [Fe 8 S 7 ] cluster complex relevant to the nitrogenase P-cluster, from a self-assembly reaction of Fe(II) bis-amide, tetramethylthiourea (tmtu), 2,4,6-triisopropylbenzenethiol (HStip), and elemental sulfur (S 8 ) in toluene [16]. We thus investigated the reactions of 4 and 5 with isocyanides and phosphines, aiming at isolation of neutral MoFe 3 S 4 clusters.…”

Section: Reactions Of [Cp * Mofe 3 S 4 X 3 ] à (X = Cl I) With P T Bmentioning

confidence: 99%

[MoFe3S4]3+ and [MoFe3S4]2+ cubane clusters containing a pentamethylcyclopentadienyl molybdenum moiety

Komuro

Kawaguchi

Liu

et al. 2007

Journal of Organometallic Chemistry

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Synthesis of the P-Cluster Inorganic Core of Nitrogenases

Cited by 107 publications

References 27 publications

Synthetic analogues of [Fe ₄ S ₄ (Cys) ₃ (His)] in hydrogenases and [Fe ₄ S ₄ (Cys) ₄ ] in HiPIP derived from all-ferric [Fe ₄ S ₄ {N(SiMe ₃ ) ₂ }
Ohki
¹
,
Tanifuji
²
,
Yamada
³

et al. 2011
Proc. Natl. Acad. Sci. U.S.A.
Self Cite
43
1
29
0
View full text Add to dashboard Cite

Synthetic analogues of [Fe ₄ S ₄ (Cys) ₃ (His)] in hydrogenases and [Fe ₄ S ₄ (Cys) ₄ ] in HiPIP derived from all-ferric [Fe ₄ S ₄ {N(SiMe ₃ ) ₂ }
Ohki
¹
,
Tanifuji
²
,
Yamada
³

et al. 2011
Proc. Natl. Acad. Sci. U.S.A.
Self Cite
43
1
29
0
View full text Add to dashboard Cite

Biosynthesis of the Metalloclusters of Molybdenum Nitrogenase

[MoFe3S4]3+ and [MoFe3S4]2+ cubane clusters containing a pentamethylcyclopentadienyl molybdenum moiety

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Synthesis of the P-Cluster Inorganic Core of Nitrogenases

Cited by 107 publications

References 27 publications

Synthetic analogues of [Fe 4 S 4 (Cys) 3 (His)] in hydrogenases and [Fe 4 S 4 (Cys) 4 ] in HiPIP derived from all-ferric [Fe 4 S 4 {N(SiMe 3 ) 2 } Ohki1, Tanifuji2, Yamada3 et al. 2011Proc. Natl. Acad. Sci. U.S.A.Self Cite431290View full textAdd to dashboardCite

Synthetic analogues of [Fe 4 S 4 (Cys) 3 (His)] in hydrogenases and [Fe 4 S 4 (Cys) 4 ] in HiPIP derived from all-ferric [Fe 4 S 4 {N(SiMe 3 ) 2 } Ohki1, Tanifuji2, Yamada3 et al. 2011Proc. Natl. Acad. Sci. U.S.A.Self Cite431290View full textAdd to dashboardCite

Biosynthesis of the Metalloclusters of Molybdenum Nitrogenase

[MoFe3S4]3+ and [MoFe3S4]2+ cubane clusters containing a pentamethylcyclopentadienyl molybdenum moiety

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Product

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About