Stoichiometric H2 production from H2O upon Mn2(CO)10 photolysis

Kee, Jun Wei; Chong, Che Chang; Toh, Chun Keong; Chong, Yuan Yi; Fan, Wai Yip

doi:10.1016/j.jorganchem.2012.10.034

Cited by 8 publications

(7 citation statements)

References 36 publications

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“…For instance, when 2 is treated with air-free water it produces a different material with an ATR-FTIR spectrum closely resembling the white material that is obtained when 1 , cymantrene, or Mn 2 (CO) 10 is irradiated in hydrocarbon/water biphasic mixtures; these ill-defined white species are not the same, but they all contain stretches in the region associated with inorganic carbonates and hydroxides moieties (Figure S3). Fan and co-workers described the solids as Mn(CO 3 ), but we believe they are complicated mixtures of ill-defined manganese salts that possibly contain OH and/or CO 3 groups.…”

Section: Resultssupporting

confidence: 57%

“…We did, however, confirm Fan and co-workers findings that H 2 is produced by the photochemical reaction between Mn 2 (CO) 10 and water in hexane (30% yield, entry 9, Table ). However, the yield of H 2 in wet toluene is small (3% yield, entry 8, Table ). In another control reaction we demonstrated that Mn 2 (CO) 10 and anhydrous [Ph 3 PO] 2 ·H 2 O 2 in benzene or toluene produce H 2 in a photochemical reaction (31% yield) providing an explanation for the steady decrease of H 2 O 2 in photochemical reactions with 1 despite the stability of [Ph 3 PO] 2 ·H 2 O 2 under irradiation by itself (vide infra).…”

Section: Resultsmentioning

confidence: 95%

“…We explored a variety of manganese carbonyl compounds within the context of Fan’s original discovery of water splitting with cymantrene and hydrogen production from water with Mn 2 (CO) 10 for comparative purposes with 1 (Table , entries 6–9). , Generally, our results are consistent with those found by Fan and co-workers. Solvents such as MeCN, tetrahydrofuran (THF), benzene, and toluene retard H 2 formation, and a majority of the compounds studied here produce H 2 O 2 in yields below 1% regardless of solvent.…”

Section: Resultsmentioning

confidence: 99%

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Photochemical Water-Splitting with Organomanganese Complexes

et al. 2017

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Certain organometallic chromophores with water-derived ligands, such as the known [Mn(CO)(μ-OH)] (1) tetramer, drew our attention as possible platforms to study water-splitting reactions. Herein, we investigate the UV irradiation of various tricarbonyl organomanganese complexes, including 1, and demonstrate that dihydrogen, CO, and hydrogen peroxide form as products in a photochemical water-splitting decomposition reaction. The organic and manganese-containing side products are also characterized. Labeling studies with O-1 suggest that the source of oxygen atoms in HO originates from free water that interacts with 1 after photochemical dissociation of CO (1-CO) constituting the oxidative half-reaction of water splitting mediated by 1. Hydrogen production from 1 is the result of several different processes, one of which involves the protons derived from the hydroxido ligands in 1 constituting the reductive half-reaction of water splitting mediated by 1. Other processes that generate H are also operative and are described. Collectively the results from the photochemical decomposition of 1 provide an opportunity to propose a mechanism, and it is discussed within the context of developing new strategies for water-splitting reactions with organomanganese complexes.

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Section: Resultssupporting

confidence: 57%

Section: Resultsmentioning

confidence: 95%

Section: Resultsmentioning

confidence: 99%

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Photochemical Water-Splitting with Organomanganese Complexes

et al. 2017

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“…Additionally, such a setup could potentially allow the integration of the H 2 evolution reaction with the oxidation half-reaction, which is typically pursued in aqueous media. However, biphasic H 2 generation has rarely been studied, and very few examples exist in literature. , …”

Section: Introductionmentioning

confidence: 99%

Light-Driven Hydrogen Generation from Microemulsions Using Metallosurfactant Catalysts and Oxalic Acid

et al. 2017

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A unique microemulsion-based photocatalytic water reduction system is demonstrated. Iridium- and rhodium-based metallosurfactants, namely, [Ir(ppy)(dhpdbpy)]Cl and [Rh(dhpdbpy)Cl]Cl (where ppy = 2-phenylpyridine and dhpdbpy = 4,4'-diheptadecyl-2,2'-bipyridine), were employed as photosensitizer and proton reducing catalyst, respectively, along with oxalic acid as a sacrificial reductant in a toluene/water biphasic mixture. The addition of 1-octylamine is proposed to initiate the reaction, by coupling with oxalic acid to form an ion pair, which acts as an additional surfactant. Concentration optimizations yielded high activity for both the photosensitizer (240 turnovers, turnover frequency (TOF) = 200 h) and catalyst (400 turnovers, TOF = 230 h), with the system generating hydrogen even after 95 h. Mechanistic insights were provided by gas-phase Raman, electrochemical, and luminescence quenching analysis, suggesting oxidative quenching to be the principle reaction pathway.

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“…Our roots in exploring the fundamental chemistry of organomanganese(I) centers originated from our interest in the finding that cymantrene [CpMn(CO) 3 ] can mediate a stoichiometric water-splitting reaction by the action of, presumably, a single photon . Using a variety of organomanganese(I) complexes with and without water-derived ligands (e.g., Chart ), we showed that only certain heteronuclear Mn I -OH complexes produce H 2 under photochemical conditions.…”

Section: Resultsmentioning

confidence: 99%

Resurgence of Organomanganese(I) Chemistry. Bidentate Manganese(I) Phosphine–Phenol(ate) Complexes

2019

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As part of the United Nations 2019 celebration of the periodic table of elements, we are privileged to present our studies with the element manganese in this Forum Article series. Catalysis with organomanganese(I) complexes has recently emerged as an important area with the discovery that pincer manganese(I) complexes that can activate substrates through metal−ligand cooperative mechanisms are active (de)hydrogenation catalysts. However, this rapidly growing field faces several challenges, and we identify these in this Forum Article. Some of our efforts in addressing these challenges include using alternative precursors to Mn(CO) 5 Br to prepare manganese(I) dicarbonyl complexes, the latter of which is usually a component of active catalysts. Specifically, the synthesis of a new bidentate phosphine−phenol ligand along with its corresponding coordination chemistry of five new manganese(I) complexes is described. The complexes having two phenol−phenolate moieties interact with the secondary coordination sphere to enable facile loss of the bromido ligand and even one of the CO ligands to afford manganese(I) dicarbonyl centers.

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Stoichiometric H2 production from H2O upon Mn2(CO)10 photolysis

Cited by 8 publications

References 36 publications

Photochemical Water-Splitting with Organomanganese Complexes

Photochemical Water-Splitting with Organomanganese Complexes

Light-Driven Hydrogen Generation from Microemulsions Using Metallosurfactant Catalysts and Oxalic Acid

Resurgence of Organomanganese(I) Chemistry. Bidentate Manganese(I) Phosphine–Phenol(ate) Complexes

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