Thiolate Bridged Nickel–Iron Complexes Containing both Iron(0) and Iron(<scp>II</scp>) Carbonyls

Lai, Chia‐Huei; Reibenspies, Joseph H.; Darensbourg, Marcetta Y.

doi:10.1002/anie.199623901

Cited by 133 publications

(83 citation statements)

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“…These are slightly different from those reported for a THF solution of [(BME-DACO)NiFe(CO) 4 ]; [16] however, they are in the same region as the CO absorption observed at 1943 cm Ϫ1 for [NiFe]-hydrogenase. [23] The 1 H NMR spectrum shows resonance signals for every proton and every methyl group, which is in agreement with the proposed asymmetric structure.…”

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confidence: 95%

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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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“…This structure, containing a square-planar low spin Ni II ion and a low spin Fe(0) moiety, is similar to that of [(BME-DACO)NiFe(CO) 4 ]. [16] In the IR spectrum of complex (2), three signals assigned to the CO groups are observed at 2009, 1945 and 1860 cm…”

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confidence: 99%

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

et al. 2003

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“…However, most of the structural models contain a mixed donor environment around nickel. A variety of square-planar nickel complexes have been synthesized with a NiS 4 chromophore [13], and several nickel-iron complexes have been synthesized relevant for hydrogenase modeling [2,11,[14][15][16][17][18]. So far only a few heterodimetallic nickel iron complexes have been reported containing an S 4 coordination environment around nickel [16,19].…”

Section: Introductionmentioning

confidence: 99%

New nickel complexes with an S4 coordination sphere; synthesis, characterization and reactivity towards nickel and iron compounds

Verhagen

Beretta

Spek

et al. 2004

Inorganica Chimica Acta

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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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Thiolate Bridged Nickel–Iron Complexes Containing both Iron(0) and Iron(II) Carbonyls

Cited by 133 publications

References 24 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

New nickel complexes with an S4 coordination sphere; synthesis, characterization and reactivity towards nickel and iron compounds

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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Thiolate Bridged Nickel–Iron Complexes Containing both Iron(0) and Iron(II) Carbonyls

Cited by 133 publications

References 24 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

New nickel complexes with an S4 coordination sphere; synthesis, characterization and reactivity towards nickel and iron compounds

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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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