Aryldiazenido (N2Ar) complexes. Carboxylate, formate, hydroxycarbonyl, and hydride derivatives of [(.eta.-C5H5)Re(CO)2(N2Ar)][BF4] and [(.eta.-C5Me5)Re(CO)2(N2Ar)][BF4] (Ar = aryl)

Barrientos-Penna, Carlos F.; Gilchrist, A. B.; Klahn, A. Hugo; Hanlan, A. J. Lee; Sutton, Derek

doi:10.1021/om00122a008

Cited by 23 publications

(11 citation statements)

References 2 publications

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“…The carboxylic group may be either cis or trans with respect to the chloro ligand. Several carboxylato-metal complexes of Ir [69] [70], Pt [71], Fe [72], and Re [73] [74] have been isolated, characterized, and their reactivity towards decarboxylation studied. Most are formed by direct attack of H,O [69] [70] or NaOH [72] [73] on coordinated CO. A hydroxycarbonyl complex of Pt (11) is obtained on insertion of CO into a metal-hydroxo bond [71].…”

Section: Generation Of the Reduced Species In The Photochemicalmentioning

confidence: 99%

Photochemical and Electrochemical Reduction of Carbon Dioxide to Carbon Monoxide Mediated by (2,2′‐Bipyridine)tricarbonylchlororhenium(I) and Related Complexes as Homogeneous Catalysts

Hawecker¹,

Lehn²,

Ziessel³

1986

Helvetica Chimica Acta

659

441

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Wac-Re(bpy) (CO),Cl] (bpy = 2,2'-bipyridine) is an efficient homogeneous catalyst for the selective and sustained photochemical or electrochemical reduction of CO, to CO. A quantum yield of 14% and a faradic efficiency of 98 % were measured in the presence of excess C1-ions.The photochemical process took place under visible-light irradiation and consumed a tertiary amine as electron donor. A formato-rhenium complex was isolated in the absence ofexcess CI-ions. Substitution by CI-ion generated free formate, but no CO was detected. Luminescence measurements showed that the tertiary amine quenches the metal-to-ligand charge-transfer excited state of the rhenium complex via a reductive mechanism, with a rate constant of 3.4 x lo7M-'S-'. The 19e-complex [Re(bpy) (CO),X]-produced either photochemically or electrochemically appears to be the active precursor in the CO-generation process. Detailed spectroscopic studies on I3C-enriched carbonyl-rhenium and formato-rhenium complexes derived from I3C-enriched C 0 2 were performed in order to confirm the origin of the products and to study the exchange of the ligands. A mechanism for the present C 0 2 photoreduction process is presented; it involves separate pathways for CO and formate generation, in which the [Re(bpy) (CO),X] complex plays the role of boih rhephotoactivr and fhe catalytic center.

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Section: Generation Of the Reduced Species In The Photochemicalmentioning

confidence: 99%

Photochemical and Electrochemical Reduction of Carbon Dioxide to Carbon Monoxide Mediated by (2,2′‐Bipyridine)tricarbonylchlororhenium(I) and Related Complexes as Homogeneous Catalysts

Hawecker¹,

Lehn²,

Ziessel³

1986

Helvetica Chimica Acta

659

441

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“…There are numerous publications dealing with mechanistic aspects of this reaction (Scheme 1). [8][9][10][11][12][13][14][15][16] The first step after the photoactivation of the rheniumcomplex (MLCT) is clearly the reductive quenching of the excited state by the sacrificial donor (tertiary amine) as it has been clarified by laser spectroscopy (Scheme 1). [8][9][10][11] This gives a short lived one electron reduced species (OER) in which a coordination site may become available by dissociation of a ligand.…”

Section: Introductionmentioning

confidence: 99%

“…The intermediates of the catalytic cycle cannot be labelled unambiguously, but at least a few carboxylato-metal complexes of rhenium have been isolated and characterized and their reactivity towards decarboxylation studied. 15,16 The formation of CO from CO 2 however requires two electrons. Therefore another electron transfer is necessary.…”

Section: Introductionmentioning

confidence: 99%

Binuclear rhenium(i) complexes for the photocatalytic reduction of CO2

et al. 2012

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Binuclear rhenium(I) complexes with 1,2-bis(4,4'-methyl-[2,2']bipyridyl)-ethane and 1,2-bis(4,4'-methyl-[2,2']bipyridyl)-dodecane as bridging ligands and their mononuclear analogues have been synthesized and characterized by their spectroscopic and electrochemical properties. First reduction potentials and luminescence properties as well as the reductive quenching of the emissive state with TEOA were not affected by the alkyl linker. By means of a detailed comparison of the photocatalytic CO(2) reductions of the monometallic and the bimetallic complexes a great beneficial effect on the activity depending on the proximity of the centres was found. In high dilution the overall kinetics in the CO(2) photoreduction of mononuclear complexes are clearly monometallic. If the proximity of the centres is adjusted according to the lifetime of the OER (one electron reduced species) the photocatalytic activity is greatly improved showing a clear bimetallic mechanism. In the binuclear rhenium complexes, both the facile generation of a free coordination site and binuclear interactions for effective two electron transfer can be realized.

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“…Subsequently, a CO 2 adduct can be formed via nucleophilic attack of the rhenium center on the electrophilic carbon atom of the CO 2 molecule (Scheme 2). The intermediates of the catalytic cycle cannot be unambiguously labeled, but at least several carboxylato-metal complexes of rhenium have been isolated, characterized, and their reactivity towards decarboxylation studied [79,80].…”

Section: Design Of the Reduction Sitementioning

confidence: 99%

Conversion of CO2 via Visible Light Promoted Homogeneous Redox Catalysis

2012

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Abstract:This review gives an overview on the principles of light-promoted homogeneous redox catalysis in terms of applications in CO 2 conversion. Various chromophores and the advantages of different structures and metal centers as well as optimization strategies are discussed. All aspects of the reduction catalyst site are restricted to CO 2 conversion. An important focus of this review is the question of a replacement of the sacrificial donor which is found in most of the current publications. Furthermore, electronic parameters of supramolecular systems are reviewed with reference to the requisite of chromophores, oxidation and reduction sites.

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Aryldiazenido (N2Ar) complexes. Carboxylate, formate, hydroxycarbonyl, and hydride derivatives of [(.eta.-C5H5)Re(CO)2(N2Ar)][BF4] and [(.eta.-C5Me5)Re(CO)2(N2Ar)][BF4] (Ar = aryl)

Abstract: The aryldiazenido complexes [(77-C5H5)Re(CO)2(p-N2C6H4R

Cited by 23 publications

References 2 publications

Photochemical and Electrochemical Reduction of Carbon Dioxide to Carbon Monoxide Mediated by (2,2′‐Bipyridine)tricarbonylchlororhenium(I) and Related Complexes as Homogeneous Catalysts

Photochemical and Electrochemical Reduction of Carbon Dioxide to Carbon Monoxide Mediated by (2,2′‐Bipyridine)tricarbonylchlororhenium(I) and Related Complexes as Homogeneous Catalysts

Binuclear rhenium(i) complexes for the photocatalytic reduction of CO2

Conversion of CO2 via Visible Light Promoted Homogeneous Redox Catalysis

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