[{(η5-C5Me5)Fe}2(μ-H)4]: A Novel Dinuclear Iron Tetrahydrido Complex

Ohki, Yasuhiro; Suzuki, Hiroharu

doi:10.1002/1521-3757(20000901)112:17<3250::aid-ange3250>3.0.co;2-8

Cited by 4 publications

(3 citation statements)

References 34 publications

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“…Synthesis of 1H . 1H was prepared using a modified version of the [{Cp*Fe} 2 (μ-H) 4 ] synthesis procedure by Suzuki and Ohki . Pentaisopropylcyclopentadienyl (dimethoxyethane) iron(II) bromide (200 mg, 0.40 mmol) was dissolved in THF (20 mL), and the yellow solution was cooled to −78 °C.…”

Section: Experimental Sectionmentioning

confidence: 99%

“…1H was prepared using a modified version of the [{Cp*Fe} 2 (μ-H) 4 ] synthesis procedure by Suzuki and Ohki. 52 Pentaisopropylcyclopentadienyl (dimethoxyethane) iron(II) bromide (200 mg, 0.40 mmol) was dissolved in THF (20 mL), and the yellow solution was cooled to −78 °C. To this solution, a suspension of lithium aluminum hydride (120 mg, 3.2 mmol) in THF (20 mL) was added, while the mixture turned red.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…These dinuclear tetra-hydrido complexes are known for C(sp 2 )−H, Si−H, 56 P−H, B−H, 57,58 and P 4 activation 55 and were described as diamagnetic, classical metal hydrides with a short Fe−Fe distance of 2.20 Å. 54 Since 1H is a 30 e − species, the noble gas rule would require an Fe−Fe triple bond between both Fe atoms, which is contradicted by Morokuma and Koga for the Ru analogue, where they claim a missing direct M−M bond. 36 Reference 1 is coordinated in a typical sandwich structure, while 1H exhibits a triple-decker structure with a planar H 4 cluster ({H 4 }) bridging both iron atoms, with an Fe−Fe S1) agree with low spin Fe +II central atoms for both complexes.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

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The Bonding Situation in the Dinuclear Tetra-Hydrido Complex [{⁵CpFe}₂(μ-H)₄] Revisited by Hard X-Ray Spectroscopy

et al. 2018

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High energy resolution fluorescence detected XANES (HERFD-XANES) and valence-to-core X-ray emission spectroscopy (VtC-XES) are introduced as powerful tools to investigate hydride–iron interaction, the possible iron–iron bond, and iron spin state of the dinuclear tetra-hydrido complex [{5CpFe}2(μ-H)4] (1H, 5Cp = η5-C5 iPr5) by thoroughly accessing the geometric and electronic structure of this complex in comparison to the nonhydride reference [5CpCpFe] (1, Cp = C5H5). The so far observed most intense hydride induced signals in the pre-edge feature of the HERFD-XANES and in the VtC-XES spectra at the iron K-edge allow a precise analysis of the LUMO and HOMO states, respectively, by application of time-dependent density function theory (TD-DFT) and density functional theory (DFT) calculations. The results of these calculations are further employed to understand the oxidation state, spin states, and potential Fe–Fe bonds in this complex.

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Section: Experimental Sectionmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

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The Bonding Situation in the Dinuclear Tetra-Hydrido Complex [{⁵CpFe}₂(μ-H)₄] Revisited by Hard X-Ray Spectroscopy

et al. 2018

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Bimetallic Activation of 2‐Alkanones through Photo‐Induced α‐Hydrogen Abstraction Mediated by a Dinuclear Ruthenium Tetrahydride Complex

et al. 2013

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The photochemical behavior of transition-metal complexes has long been a fascinating subject that is related to electron transfer processes, specific organotransformations, photosynthesis, and electrochemical conversion of solar energy. Although there are a vast number of studies on the photochemistry of mononuclear complexes, multimetallic systems remain unexplored. [1] In general, in cluster complexes with metal-metal bonds, the lowest unoccupied orbital is an antibonding orbital that is delocalized over the metal framework. Whereas mononuclear polyhydride complexes often eliminate hydride ligands as dihydrogen, the elimination of dihydrogen upon photoirradation is hindered in hydride-bridged clusters. As a result, fragmentation of the metal framework of polyhydridebridged clusters upon photoinduced single electron excitation is suppressed. Therefore, cluster effects, that is, multiple interactions between the substrate and metal sites, are still anticipated, even in the photoexcited state of the polyhydride cluster. These characteristic features of polyhydride-bridged clusters may result in rather exotic photochemical behavior.We have studied the synthesis of homo-and heterometallic polyhydride cluters and have reported their reaction chemistry under thermal conditions.[2] Some remarkable reactions performed on the reaction sites of these polyhydride clusters were recently highlighted by Lavigne.[3] To extend our research to a new area, we began a project on the photochemistry of a polyhydride cluster which we anticipated to possess increased structural stability.We report herein an unusual photochemical reaction of a diruthenium tetrahydride complex, [(Cp*Ru)(m-H) 4 -(RuCp*)] (1) (Cp* = h 5 -C 5 Me 5 ), with 2-alkanones, which produces dinuclear oxatrimethylenemethane (OTMM) complexes. Upon irradiation with UV light (365 nm) at 10 8C for 48 h under an argon atmosphere, the red suspension of diruthenium tetrahydride (46.1 mg, 96.7 mmol) in acetone (15 mL) became a blue-purple solution. Removal of the solvent under reduced pressure, followed by purification of residual solids by column chromatography on alumina (Merck Aluminium Oxide 90 standardized) with a toluene/tetrahydrofuran (5:1) mixture afforded a dinuclear OTMM complex of ruthenium, [(Cp*Ru){m-h 3 :h 1 -(CH 2 ) 2 CO}(m-H) 2 (RuCp*)] (2 a), in 91 % yield (46.8 mg, 88.2 mmol; Scheme 1).The 1 H NMR spectrum of 2 a recorded in [D 6 ]benzene at 25 8C exhibited two singlet signals at d = 1.67 and 1.80 ppm, which were assignable to the Cp* groups. Two singlet-like signals for the methylene protons of the OTMM ligand appeared at d = 1.22 (2 H, w1 = 2 = 1.4 Hz, anti to the O atom) and 3.07 ppm (2 H, w1 = 2 = 2.1 Hz, syn to the O atom). A signal corresponding to the chemically equivalent bridging hydride ligands was observed at d = À12.18 ppm (s, 2 H, w1 = 2 = 13.5 Hz). A COSY and selective decoupling experiment showed the spin-coupling interactions among the anti, syn, and Ru-bound protons.[4] The 13 C NMR data fully supported the structure of 2 a: the sign...

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Bimetallic Activation of 2‐Alkanones through Photo‐Induced α‐Hydrogen Abstraction Mediated by a Dinuclear Ruthenium Tetrahydride Complex

Suzuki¹,

Shimogawa²,

Muroi³

et al. 2013

Angew Chem Int Ed

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The photochemical behavior of transition-metal complexes has long been a fascinating subject that is related to electron transfer processes, specific organotransformations, photosynthesis, and electrochemical conversion of solar energy. Although there are a vast number of studies on the photochemistry of mononuclear complexes, multimetallic systems remain unexplored. [1] In general, in cluster complexes with metal-metal bonds, the lowest unoccupied orbital is an antibonding orbital that is delocalized over the metal framework. Whereas mononuclear polyhydride complexes often eliminate hydride ligands as dihydrogen, the elimination of dihydrogen upon photoirradation is hindered in hydride-bridged clusters. As a result, fragmentation of the metal framework of polyhydridebridged clusters upon photoinduced single electron excitation is suppressed. Therefore, cluster effects, that is, multiple interactions between the substrate and metal sites, are still anticipated, even in the photoexcited state of the polyhydride cluster. These characteristic features of polyhydride-bridged clusters may result in rather exotic photochemical behavior.We have studied the synthesis of homo-and heterometallic polyhydride cluters and have reported their reaction chemistry under thermal conditions. [2] Some remarkable reactions performed on the reaction sites of these polyhydride clusters were recently highlighted by Lavigne. [3] To extend our research to a new area, we began a project on the photochemistry of a polyhydride cluster which we anticipated to possess increased structural stability.We report herein an unusual photochemical reaction of a diruthenium tetrahydride complex, [(Cp*Ru)(m-H) 4 -(RuCp*)] (1) (Cp* = h 5 -C 5 Me 5 ), with 2-alkanones, which produces dinuclear oxatrimethylenemethane (OTMM) complexes.Upon irradiation with UV light (365 nm) at 10 8C for 48 h under an argon atmosphere, the red suspension of diruthenium tetrahydride (46.1 mg, 96.7 mmol) in acetone (15 mL) became a blue-purple solution. Removal of the solvent under reduced pressure, followed by purification of residual solids by column chromatography on alumina (Merck Aluminium Oxide 90 standardized) with a toluene/tetrahydrofuran (5:1) mixture afforded a dinuclear OTMM complex of ruthenium, [(Cp*Ru){m-h 3 :h 1 -(CH 2 ) 2 CO}(m-H) 2 (RuCp*)] (2 a), in 91 % yield (46.8 mg, 88.2 mmol; Scheme 1).The 1 H NMR spectrum of 2 a recorded in [D 6 ]benzene at 25 8C exhibited two singlet signals at d = 1.67 and 1.80 ppm, which were assignable to the Cp* groups. Two singlet-like signals for the methylene protons of the OTMM ligand appeared at d = 1.22 (2 H, w1 = 2 = 1.4 Hz, anti to the O atom) and 3.07 ppm (2 H, w1 = 2 = 2.1 Hz, syn to the O atom). A signal corresponding to the chemically equivalent bridging hydride ligands was observed at d = À12.18 ppm (s, 2 H, w1 = 2 = 13.5 Hz). A COSY and selective decoupling experiment showed the spin-coupling interactions among the anti, syn, and Ru-bound protons. [4] The 13 C NMR data fully supported the structure of 2 a: the signa...

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[{(η5-C5Me5)Fe}2(μ-H)4]: A Novel Dinuclear Iron Tetrahydrido Complex

Cited by 4 publications

References 34 publications

The Bonding Situation in the Dinuclear Tetra-Hydrido Complex [{⁵CpFe}₂(μ-H)₄] Revisited by Hard X-Ray Spectroscopy

The Bonding Situation in the Dinuclear Tetra-Hydrido Complex [{⁵CpFe}₂(μ-H)₄] Revisited by Hard X-Ray Spectroscopy

Bimetallic Activation of 2‐Alkanones through Photo‐Induced α‐Hydrogen Abstraction Mediated by a Dinuclear Ruthenium Tetrahydride Complex

Bimetallic Activation of 2‐Alkanones through Photo‐Induced α‐Hydrogen Abstraction Mediated by a Dinuclear Ruthenium Tetrahydride Complex

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[{(η5-C5Me5)Fe}2(μ-H)4]: A Novel Dinuclear Iron Tetrahydrido Complex

Cited by 4 publications

References 34 publications

The Bonding Situation in the Dinuclear Tetra-Hydrido Complex [{5CpFe}2(μ-H)4] Revisited by Hard X-Ray Spectroscopy

The Bonding Situation in the Dinuclear Tetra-Hydrido Complex [{5CpFe}2(μ-H)4] Revisited by Hard X-Ray Spectroscopy

Bimetallic Activation of 2‐Alkanones through Photo‐Induced α‐Hydrogen Abstraction Mediated by a Dinuclear Ruthenium Tetrahydride Complex

Bimetallic Activation of 2‐Alkanones through Photo‐Induced α‐Hydrogen Abstraction Mediated by a Dinuclear Ruthenium Tetrahydride Complex

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The Bonding Situation in the Dinuclear Tetra-Hydrido Complex [{⁵CpFe}₂(μ-H)₄] Revisited by Hard X-Ray Spectroscopy

The Bonding Situation in the Dinuclear Tetra-Hydrido Complex [{⁵CpFe}₂(μ-H)₄] Revisited by Hard X-Ray Spectroscopy