Novel anionic rearrangements in hexacarbonyldiiron complexes of chelating organosulfur ligands

Seyferth, Dietmar; Womack, Gary B.; Gallagher, Michael; Cowie, Martin; Hames, Barry W.; Fackler, John P.; Mazany, Anthony M.

doi:10.1021/om00145a009

Cited by 99 publications

(93 citation statements)

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“…[22,36,44] As observed in 1, PDSe, and PDTe, the C2 methylene group of 2 and 3 is disordered over two positions with 50 % probability. [22,36,44] Disorder also is likely between the location of the chalcogen atoms, especially in the case of the S and Se atoms of molecule 2, where the Fe-Se and Figure 1. ORTEP drawing of [Fe 2 (µ-SC 3 H 6 Se-µ)(CO) 6 ] (2) at the 50 % probability level (hydrogen atoms are omitted for clarity).…”

Section: Resultsmentioning

confidence: 87%

“…The central [2FeSX] (X = Se, Te) moieties of 2 and 3 are in the butterfly conformation, and the coordination geometry around the iron cores is rather similar to those reported for 1 and for the PDSe and PDTe complexes. [22,36,44] The FeFe distances increase according to the trend 1 Ͻ 2 Ͻ PDSe Ͻ 3 Ͻ PDTe [with values of 2.5103(11) Ͻ 2.5373(9) Ͻ 2.5610(8) Ͻ 2.5736(10) Ͻ 2.633(1) Å, respectively], which is attributed to the increase in the atom size from S through Se to Te. [22,36,44] As observed in 1, PDSe, and PDTe, the C2 methylene group of 2 and 3 is disordered over two positions with 50 % probability.…”

Section: Resultsmentioning

confidence: 99%

“…[22,36,44] The FeFe distances increase according to the trend 1 Ͻ 2 Ͻ PDSe Ͻ 3 Ͻ PDTe [with values of 2.5103(11) Ͻ 2.5373(9) Ͻ 2.5610(8) Ͻ 2.5736(10) Ͻ 2.633(1) Å, respectively], which is attributed to the increase in the atom size from S through Se to Te. [22,36,44] As observed in 1, PDSe, and PDTe, the C2 methylene group of 2 and 3 is disordered over two positions with 50 % probability. [22,36,44] Disorder also is likely between the location of the chalcogen atoms, especially in the case of the S and Se atoms of molecule 2, where the Fe-Se and Figure 1.…”

Section: Resultsmentioning

confidence: 99%

“…These data are in the typical range of such model complexes. [16,17,20,22,24,36,[47][48][49] For comparison, the carbonyl stretching frequencies of the all-sulfur PDT molecule 1 measured under the same conditions are in the range 2074-1990 cm -1 . The down-shifting of the CO absorption bands to lower frequencies from 1 through 2 to 3 is an indication of the increased π back-donation between the diiron center and the CO ligand caused by the rising donor ability of the chalcogen from S through Se to Te.…”

Section: Resultsmentioning

confidence: 99%

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Synthesis and Characterization of [FeFe]‐Hydrogenase Models with Bridging Moieties Containing (S, Se) and (S, Te)

et al. 2010

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Section: Resultsmentioning

confidence: 87%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

See 2 more Smart Citations

Synthesis and Characterization of [FeFe]‐Hydrogenase Models with Bridging Moieties Containing (S, Se) and (S, Te)

et al. 2010

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“…On an entirely different time scale, chemists have established the ability of the diirondisulfide of (-S 2 )Fe 2 (CO) 6 unit to mediate organic transformations at sulfur (33,34), including the synthesis of model complexes (35) of import to the discussion below. The parent model, (-pdt)Fe 2 (CO) 6 (35) is a complex that reproduces the Fe 2 S 2 core fairly faithfully (36), including the three-light-atom S-to-S linker (Fig.…”

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confidence: 99%

The organometallic active site of [Fe]hydrogenase: Models and entatic states

Darensbourg

Lyon

Zhao

et al. 2003

Proc. Natl. Acad. Sci. U.S.A.

271

201

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The simple organometallic, (-S2)Fe2(CO)6, serves as a precursor to synthetic analogues of the chemically rudimentary iron-only hydrogenase enzyme active site. The fundamental properties of the (-SCH 2CH2CH2S)[Fe(CO)3]2 compound, including structural mobility and regioselectivity in cyanide͞carbon monoxide substitution reactions, relate to the enzyme active site in the form of transition-state structures along reaction paths rather than ground-state structures. Even in the absence of protein-based active-site organization, the ground-state structural model complexes are shown to serve as hydrogenase enzyme reaction models, H 2 uptake and H2 production, with the input of photoor electrochemical energy, respectively.

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CO- und CN−-Liganden in einem klassischen metallorganischen Komplexmodell für reine Eisen-Hydrogenasen

et al. 1999

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Wie bei der gut charakterisierten [NiFe]-Hydrogenase [1] deuten IR-spektroskopische Untersuchungen [2] und Kristallstrukturanalysen von reinen [Fe]-Hydrogenasen, die aus Clostridium pasteurianum [3] und Desulfovibrio desulfuricans [4] isoliert wurden, darauf hin, daû das aktive Zentrum zweiatomige Liganden, CN À und CO, enthält. Die in Abbildung 1 gezeigte Strukturformel vereint Merkmale des Dieisenzentrums beider reinen [Fe]-Hydrogenase-Strukturen. So war Abbildung 1. Oben: Das zweikernige Eisenzentrum von reinen [Fe]-Hydrogenasen als eine Verschmelzung von zwei bekannten Strukturen. [3, 4] Unten: Ausschnitt (Dreifachbindungsbereich) des IR-Spektrums von der oxidierten Form von Desulfovibrio vulgaris. (Spektrum wiedergegeben nach Lit. [2].)z. B. in der erstgenannten Struktur die S-S-Verknüpfung nicht als Kohlenwasserstoffbrücke (CH 2 ) 3 ausgewiesen, [3] während für die andere der dritte überbrückende Ligand nicht als CO-Gruppe angegeben wurde, [4] eine Folgerung, die mit IR-Spektren einer reinen [Fe]-Hydrogenase aus einer weiteren Quelle, Desulfovibrio vulgaris, im Einklang steht (Abbildung 1, unten). [2] Während die ¾hnlichkeit der Peptidsequenz am H-Cluster in den unterschiedlichen reinen [Fe]-Hydrogenasen dieses Mischen der Strukturen befürworten würde, [4] könnten die ¾nderungen in der n(CO)-und n(CN)-Region des IR-Spektrums bei verschiedenen Manipulationen des Proteins [2] auf möglicherweise unterschiedliche Formen der zweikernigen Einheit des aktiven Zentrums hindeuten. Die Entwicklung organometallischer Komplexe als Modelle für die spektroskopische Untersuchung ist deshalb ein wichtiges Ziel, da die Schwingungsspektroskopie ein sehr nützliches Hilfsmittel zur Bestimmung der elektronischen Faktoren ist, die die Struktur und Reaktivität in der traditionellen Organometallchemie kontrollieren.Die ¾hnlichkeit zwischen dem klassischen organometallischen Komplex [(h 5 -C 5 H 5 )Fe(CO)(CN) 2 ] À und dem Eisenzentrum der [NiFe]-Hydrogenase [5] scheint gleichermaûen bei einem homo-zweikernigen organometallischen Mimetikum des einzigartigen Dieisenzentrums in den reinen [Fe]-Hydrogenasen zu bestehen. Der Komplex [(m-pdt)Fe 2 (CO) 6 ] [6] (pdt SCH 2 CH 2 CH 2 S) gehört zu einer gut untersuchten Gruppe von [(m-SR) 2 Fe 2 (CO) 6Àx L x ]-Komplexen, die thermodynamische Senken in der Chemie niedervalenter Eisen-Thiolat-Komplexe darstellen. Hier berichten wir über seine Molekülstruktur und Untersuchungen zur CO-Labilität und Reaktivität, die zur Herstellung spektroskopisch relevanter mono-und dianionischer Cyanodimetallkomplexe führt.Aus Pentan wurden orangefarbene, plättchenförmige Kristalle von [(m-pdt)Fe 2 (CO) 6 ] erhalten (Raumgruppe P2 1 /m). [7] Die Molekülstruktur der Verbindung ist in Abbildung 2 (oben) wiedergegeben. Die Abstände und Winkel gleichen

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Novel anionic rearrangements in hexacarbonyldiiron complexes of chelating organosulfur ligands

Cited by 99 publications

References 1 publication

Synthesis and Characterization of [FeFe]‐Hydrogenase Models with Bridging Moieties Containing (S, Se) and (S, Te)

Synthesis and Characterization of [FeFe]‐Hydrogenase Models with Bridging Moieties Containing (S, Se) and (S, Te)

The organometallic active site of [Fe]hydrogenase: Models and entatic states

CO- und CN−-Liganden in einem klassischen metallorganischen Komplexmodell für reine Eisen-Hydrogenasen

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