Synthesis, X-ray structure and electrochemical characterisation of a binuclear thiolate bridged Ni–Fe–nitrosyl complex, related to the active site of NiFe hydrogenase

Osterloh, Frank E.; Saak, Wolfgang; Haase, Detlev; Pohl, Siegfried

doi:10.1039/a700884h

Cited by 90 publications

(57 citation statements)

References 21 publications

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“…This structure, containing a square-planar low spin Ni II ion and a low spin [Fe(NO) 2 ] moiety, is similar to that of the Ni-Fe-nitrosyl complex reported by Osterloh et al [15] In the IR spectrum, strong signals assigned to the NO groups are clearly observed at 1771 and 1733 cm…”

Section: Proposed Structure Of [Ni(xbsms)fe(no) 2 ] (3)supporting

confidence: 60%

“…From the geometry around the iron centre, it can be concluded that the iron centre is in a high spin state. This (15) observation has been confirmed by the room temperature magnetic susceptibility measurements, which give a µ eff value of 5.35 µ B per iron centre. This is consistent with a high spin Fe II centre without any interaction between the two iron centres in the molecule.…”

Section: Introductionsupporting

confidence: 65%

“…These absorptions are at significantly higher energies compared with those in the reported complex (1663 and 1624 cm Ϫ1 ), [15] and are also shifted relative to the starting Fe complex [Fe(CO) 2 ). [17] The NO stretches in the IR spectrum are in the range reported for linearly coordinated NO ϩ molecules.…”

mentioning

confidence: 82%

“…This is consistent with a high spin Fe II centre without any interaction between the two iron centres in the molecule. [22] The FeϪSϪNi angles of 80.301 (14) and 82.005 (15)°lead to a NiϪFe distance of 3.0403(3) Å . All distances and angles around the nickel centre are consistent with data of similar complexes in the literature.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and Characterisation of New Nickel‐Iron Complexes with an S₄ Coordination Environment around the Nickel Centre

et al. 2003

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The nickel complex [Ni(xbsms) crystallises in the monoclinic space group P2 1 /c, with the dimer located on the inversion centre. The nickel ions are in a square-planar S 2 SЈ 2 environment, comprised of two thioether and two thiolate sulfur atoms. The thiolate sulfur atoms form a bridge between the nickel ion and the iron centre. The iron ions are in a pseudo square-pyramidal S 2 Cl 3 environment, with two chloride ions forming a bridge between the two iron centres.

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Section: Proposed Structure Of [Ni(xbsms)fe(no) 2 ] (3)supporting

confidence: 60%

Section: Introductionsupporting

confidence: 65%

mentioning

confidence: 82%

Section: Introductionmentioning

confidence: 99%

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Synthesis and Characterisation of New Nickel‐Iron Complexes with an S₄ Coordination Environment around the Nickel Centre

et al. 2003

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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.…”

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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

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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Ein Strukturmodell für reine [Fe]-Hydrogenasen

et al. 1998

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In unterschiedlichen Spinzuständen liegen die beiden Fe‐Atome des asymmetrischen Zweikernkomplexes 1 vor, wie Mößbauer‐spektroskopisch nachgewiesen wurde. Der Komplex ist ein erstes Strukturmodell für reine [Fe]‐Hydrogenasen; er enthält die für biologische Systeme ungewöhnlichen, aber bei einer [NiFe]‐Hydrogenase nachgewiesenen CO‐Liganden. Die Schwingungsfrequenzen dieser Liganden stimmen gut mit denen reiner [Fe]‐Hydrogenasen überein.

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Synthesis, X-ray structure and electrochemical characterisation of a binuclear thiolate bridged Ni–Fe–nitrosyl complex, related to the active site of NiFe hydrogenase

Cited by 90 publications

References 21 publications

Synthesis and Characterisation of New Nickel‐Iron Complexes with an S₄ Coordination Environment around the Nickel Centre

Synthesis and Characterisation of New Nickel‐Iron Complexes with an S₄ Coordination Environment around the Nickel Centre

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

Ein Strukturmodell für reine [Fe]-Hydrogenasen

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Synthesis, X-ray structure and electrochemical characterisation of a binuclear thiolate bridged Ni–Fe–nitrosyl complex, related to the active site of NiFe hydrogenase

Cited by 90 publications

References 21 publications

Synthesis and Characterisation of New Nickel‐Iron Complexes with an S4 Coordination Environment around the Nickel Centre

Synthesis and Characterisation of New Nickel‐Iron Complexes with an S4 Coordination Environment around the Nickel Centre

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

Ein Strukturmodell für reine [Fe]-Hydrogenasen

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Synthesis and Characterisation of New Nickel‐Iron Complexes with an S₄ Coordination Environment around the Nickel Centre

Synthesis and Characterisation of New Nickel‐Iron Complexes with an S₄ Coordination Environment around the Nickel Centre

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