[(C6H4S2)Ni(-‘S3')Fe(CO)(PMe3)2]: A Dinuclear [NiFe] Complex Modeling the [(RS)2Ni(-SR)2Fe(CO)(L)2] Core of [NiFe] Hydrogenase Centers

Sellmann, Dieter; Geipel, Franz; Lauderbach, Frank; Heinemann, Frank W.

doi:10.1002/1521-3773(20020215)41:4<632::aid-anie632>3.3.co;2-t

Cited by 20 publications

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“…7) [75]. These complexes are indeed excellent electrocatalyts for proton [39], Evans [40], Schrö der [41], Sellmann [42], Tatsumi [43], Koch [44] and Bouwman [45].…”

Section: Hydrogenase Model Compoundsmentioning

confidence: 99%

Bioinspired catalysis at the crossroads between biology and chemistry: A remarkable example of an electrocatalytic material mimicking hydrogenases

Fontecave

Artero

2010

Comptes Rendus. Chimie

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“…7) [75]. These complexes are indeed excellent electrocatalyts for proton [39], Evans [40], Schrö der [41], Sellmann [42], Tatsumi [43], Koch [44] and Bouwman [45].…”

Section: Hydrogenase Model Compoundsmentioning

confidence: 99%

Bioinspired catalysis at the crossroads between biology and chemistry: A remarkable example of an electrocatalytic material mimicking hydrogenases

Fontecave

Artero

2010

Comptes Rendus. Chimie

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“…Well-de®ned transition metal complexes with heteroatomdonor ligands can serve as viable models for the active sites of metalloenzymes (Darensbourg et al, 2000;Kaasjager et al, 1998;Sellmann et al, 2002). Our goal is to synthesize a dinuclear NiÐFe complex that resembles the S-bridged NiÐ Fe unit of the [NiFe]-hydrogenases (Darensbourg et al, 2000).…”

Section: Commentmentioning

confidence: 99%

Bis[(3,5-dimethylpyrazol-1-yl)ethyl] disulfide

et al. 2003

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Key indicatorsSingle-crystal X-ray study T = 150 K Mean '(C±C) = 0.003 A Ê R factor = 0.038 wR factor = 0.101 Data-to-parameter ratio = 19.9For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e. # 2003 International Union of Crystallography Printed in Great Britain ± all rights reservedIn the title compound, C 14 H 22 N 4 S 2 , a diethyl disul®de bridge containing an SÐS bond of 2.0396 (6) A Ê connects two 3,5-dimethylpyrazole rings via the N1 atoms. The disul®de molecules are linked by weak CÐHÁ Á Á%(pyrazole) interactions into chains that propagate along the b direction. CommentWell-de®ned transition metal complexes with heteroatomdonor ligands can serve as viable models for the active sites of metalloenzymes (Darensbourg et al., 2000;Kaasjager et al., 1998;Sellmann et al., 2002). Our goal is to synthesize a dinuclear NiÐFe complex that resembles the S-bridged NiÐ Fe unit of the [NiFe]-hydrogenases (Darensbourg et al., 2000). The N,S-chelating ligand 1-(2-sulfanylethyl)-3,5-dimethylpyrazole (Hetdmp), which contains a thiol group to mimic cysteine residues, is well suited for this application (Bouwman & Reedijk, 1998). Colourless needles of the title compound, bis[(3,5-dimethylpyrazol-1-yl)ethyl] disul®de [or 1,1 H -dithiodiethylenebis(3,5-dimethylpyrazole)], (I), the product of ligand oxidation, were isolated in our attempts to crystallize [Ni(etdmp) 2 ], a mononuclear precursor to the desired NiÐFe model compound.A view of (I) is presented in Fig. 1, and selected geometric parameters are listed in Table 1. In (I), two 3,5-dimethylpyrazole rings are connected, via N11 and N21 (N1 of the two rings by IUPAC convention), by a diethyl disul®de bridge. The bond lengths and angles involving the disul®de group [SÐS = 2.0396 (6) A Ê , SÐC = 1.8097 (15) with respect to the disul®de bond. Thus, the pyrazole rings are nearly parallel, the dihedral angle between their planes being 6.26 (10) . Although the two 1-thioethylene-3,5-dimethyl-

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“…1), which has attracted inorganic and organometallic chemists attempting to model both the structure and physicochemical properties. Thiolate-bridged Ni-Fe complexes have been synthesized as structural models of the active site (16)(17)(18)(19)(20)(21)(22)(23)(24)(25)(26), and sulfurligated mono-and dinuclear transition metal complexes have been reported to promote H 2 activation mimicking the function of [NiFe] hydrogenase (27)(28)(29)(30)(31)(32)(33)(34)(35)(36)(37)(38)(39)(40)(41). However, synthesis of better structural/functional models remains challenging.…”

mentioning

confidence: 99%

A model for the CO-inhibited form of [NiFe] hydrogenase: synthesis of (CO) ₃ Fe( μ -S ^t Bu) ₃ Ni{SC ₆ H ₃ -2,6-(mesityl) ₂ } and reversible CO addition at the Ni site

Ohki

Yasumura

Ando

et al. 2010

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

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A [NiFe] hydrogenase model compound having a distorted trigonal-pyramidal nickel center, ðCOÞ 3 Feðμ-S t BuÞ 3 NiðSDmpÞ, 1 (Dmp¼ C 6 H 3 -2;6-ðmesitylÞ 2 ), was synthesized from the reaction of the tetranuclear Fe-Ni-Ni-Fe complex ½ðCOÞ 3 Feðμ-S t BuÞ 3 Ni 2 ðμ-BrÞ 2 , 2 with NaSDmp at −40°C. The nickel site of complex 1 was found to add CO or CN t Bu at −40°C to give ðCOÞ 3 FeðS t BuÞðμ-S t BuÞ 2 NiðCOÞ ðSDmpÞ, 3, or ðCOÞ 3 FeðS t BuÞðμ-S t BuÞ 2 NiðCN t BuÞðSDmpÞ, 4, respectively. One of the CO bands of 3, appearing at 2055cm −1 in the infrared spectrum, was assigned as the Ni-CO band, and this frequency is comparable to those observed for the CO-inhibited forms of [NiFe] hydrogenase. Like the CO-inhibited forms of [NiFe] hydrogenase, the coordination of CO at the nickel site of 1 is reversible, while the CN t Bu adduct 4 is more robust.iron | nickel | thiolates B iological hydrogen evolution and uptake are mediated by hydrogenase enzymes (1-7). The most prevalent family are the [NiFe] hydrogenases, and various forms have been identified (8)(9)(10)(11)(12)(13)(14)(15). A unique feature of the [NiFe] hydrogenase is the common organometallic dinuclear Ni-Fe frame at the active site ( Fig. 1), which has attracted inorganic and organometallic chemists attempting to model both the structure and physicochemical properties. Thiolate-bridged Ni-Fe complexes have been synthesized as structural models of the active site (16-26), and sulfurligated mono-and dinuclear transition metal complexes have been reported to promote H 2 activation mimicking the function of [NiFe] hydrogenase (27-41). However, synthesis of better structural/functional models remains challenging.One interesting aspect of the [NiFe] hydrogenase is the reversible inhibition of the active site by CO. According to a crystallographic analysis of the CO-inhibited form of the [NiFe] hydrogenase obtained from Desulfovibrio vulgaris Miyazaki F (D. v. Miyazaki F), a CO molecule is coordinated at the nickel center (42). It has been suggested that this nickel-bound CO can be liberated and the catalytic activity recovered, upon flushing with a stream of N 2 (43), or by white-light irradiation at 20 K (44). Herein we report the synthesis of a thiolate-bridged dinuclear Ni-Fe complex ðCOÞ 3 Feðμ-S t BuÞ 3 NiðSDmpÞ, 1, carrying a bulky thiolate SDmp (Dmp¼C 6 H 3 -2;6-ðmesitylÞ 2 ) at Ni, and its CO and CN t Bu adducts, ðCOÞ 3 FeðS t BuÞðμ-S t BuÞ 2 NiðCOÞðSDmpÞ, 3, and ðCOÞ 3 FeðS t BuÞðμ-S t BuÞ 2 NiðCN t BuÞðSDmpÞ, 4. The reaction of 1 with CO occurs reversibly to give 3, while the analogous CN t Bu adduct 4 is robust. We also report the x-ray crystal structures of 1, 3, and 4. Results and DiscussionSynthesis and Structure of ðCOÞ 3 Feðμ-S t BuÞ 3 NiðSDmpÞ, 1. We have reported that a linear tetranuclear Fe-Ni-Ni-Fe complex ½ðCOÞ 3 Feðμ-S t BuÞ 3 Ni 2 ðμ-BrÞ 2 , 2, which was synthesized from FeBr 2 ðCOÞ 4 þNaðS t BuÞþNiBr 2 ðEtOHÞ 4 (1∶2∼3∶1), serves as a convenient precursor for the synthesis of thiolate-bridged dinuclear Ni-Fe complexes (17). The penta-coo...

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[(C6H4S2)Ni(-‘S3')Fe(CO)(PMe3)2]: A Dinuclear [NiFe] Complex Modeling the [(RS)2Ni(-SR)2Fe(CO)(L)2] Core of [NiFe] Hydrogenase Centers

Cited by 20 publications

References 0 publications

Bioinspired catalysis at the crossroads between biology and chemistry: A remarkable example of an electrocatalytic material mimicking hydrogenases

Bioinspired catalysis at the crossroads between biology and chemistry: A remarkable example of an electrocatalytic material mimicking hydrogenases

Bis[(3,5-dimethylpyrazol-1-yl)ethyl] disulfide

A model for the CO-inhibited form of [NiFe] hydrogenase: synthesis of (CO) ₃ Fe( μ -S ^t Bu) ₃ Ni{SC ₆ H ₃ -2,6-(mesityl) ₂ } and reversible CO addition at the Ni site

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[(C6H4S2)Ni(-‘S3')Fe(CO)(PMe3)2]: A Dinuclear [NiFe] Complex Modeling the [(RS)2Ni(-SR)2Fe(CO)(L)2] Core of [NiFe] Hydrogenase Centers

Cited by 20 publications

References 0 publications

Bioinspired catalysis at the crossroads between biology and chemistry: A remarkable example of an electrocatalytic material mimicking hydrogenases

Bioinspired catalysis at the crossroads between biology and chemistry: A remarkable example of an electrocatalytic material mimicking hydrogenases

Bis[(3,5-dimethylpyrazol-1-yl)ethyl] disulfide

A model for the CO-inhibited form of [NiFe] hydrogenase: synthesis of (CO) 3 Fe( μ -S t Bu) 3 Ni{SC 6 H 3 -2,6-(mesityl) 2 } and reversible CO addition at the Ni site

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A model for the CO-inhibited form of [NiFe] hydrogenase: synthesis of (CO) ₃ Fe( μ -S ^t Bu) ₃ Ni{SC ₆ H ₃ -2,6-(mesityl) ₂ } and reversible CO addition at the Ni site