Electrochemistry and spectroelectrochemistry in indium(III) porphyrins. Reactions of five-coordinate ionic complexes

Kadish, Karl M.; Cornillon, J. L.; Cocolios, P.; Tabard, Alain; Guilard, Roger

doi:10.1021/ic00216a034

Cited by 22 publications

(14 citation statements)

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“…Instead, the initial step could be the concerted reduction of the catalyst and protonation of an anionic axial ligand as this reaction has been observed for p-block MP, followed by dissociation from the complex. 44 , 45 …”

Section: Resultsmentioning

confidence: 99%

Determinant Role of Electrogenerated Reactive Nucleophilic Species on Selectivity during Reduction of CO₂ Catalyzed by Metalloporphyrins

Göttle

Koper

2018

J. Am. Chem. Soc.

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This work provides insights to understand the selectivity during the reduction of CO2 with metalloporphyrin (MP) catalysts. The attack of a nucleophile on the carbon of the CO2 appears as an important event that triggers the catalytic reaction, and the nature of this nucleophile determines the selectivity between CO (or further reduced species) and HCOOH/HCOO–. For MP, the possible electrogenerated nucleophiles are the reduced metal-center and the hydride donor species, metal-hydride and phlorin-hydride ligand. The reduced metal-center activates the CO2 with the formation of the metal–carbon bond, which then gives rise to the formation of CO. The hydride donor species trigger the CO2 reduction by the attack of the hydride on the carbon of the CO2 (formation of a C–H bond), which results in the formation of HCOOH/HCOO– (formation of the metal-bonded formate intermediate is not involved). The MP with the metals Ni, Cu, Zn, Pd, Ag, Cd, Ga, In, and Sn are predicted to only form the phlorin-hydride intermediate and are thus suitable to produce HCOOH/HCOO–. This agrees well with the available experimental results. The MP with the metals Fe, Co, and Rh can form both the reduced-metal center and the hydride donor species (metal-hydride and phlorin-hydride), and thus are able to form both CO and HCOOH/HCOO–. The production of CO for Fe and Co is indeed observed experimentally, but not for Rh, probably due to the presence of axial ligands that may hinder the formation of the metal-bonded intermediates and thus drive the CO2RR to HCOOH/HCOO– via the phlorin intermediate.

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Section: Resultsmentioning

confidence: 99%

Determinant Role of Electrogenerated Reactive Nucleophilic Species on Selectivity during Reduction of CO₂ Catalyzed by Metalloporphyrins

Göttle

Koper

2018

J. Am. Chem. Soc.

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“…The difference in the selectivity patterns between In(0EP)CI and InTPPCl may be due to the increased basicity of the porphyrin ring in In(0EP)CI . 24 As In"' and AP' tend to form stable complexes with fluoride ion, it is considered that InTPPCl or AlTPPCl preferentially coordinates Fwith relatively high affinity. Indeed, the potentiometric selectivity coefficients of the InTPPCl-and AITPPCI-based electrodes for N02-with respect to F-ion Table 1 Potentiometric selectivity coefficients of electrodes based on different carriers.…”

Section: Potentiometric Anion Response Characteristics Of Electrodesmentioning

confidence: 99%

Nitrite-sensitive liquid membrane electrodes based on metalloporphyrin derivatives

Gao¹,

Gu²,

Yu³

et al. 1995

Analyst

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“…The second and the third reversible oxidations of 1 and 2 occur at similar potentials which are similar to that observed for TPPInCl in CH 2 Cl 2 . [11] This type of three electrooxidation process has been reported for indium(iii) ± porphyrins with metal ± metal s bonds, for example [TPPInRe(CO) 5 ] (TPP tetraphenylporphyrin). [12] As in [TPPInRe(CO) 5 ], the oxidation of 1 and 2 can be rationalized by the initial formation of an unstable singly oxidized product 9 ]} for 2), followed by a rapid In À N bond cleavage to yield [TTPIn III ] 2 and further oxidation to [TTPIn III ] 3 .…”

Section: Resultsmentioning

confidence: 68%

Synthesis and Nonlinear Optical Absorption of Novel Porphyrin–Osmium‐Cluster Complexes

Guo

Ang

Chng

et al. 2003

Chemistry A European J

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Reaction of azido(tetra-p-tolylporphyrinato)indium(III) [TTPInN(3)] and [Os(3)(mu-H)(2)(CO)(10)] in toluene at 80 degrees C overnight gave two major products, complexes 1 and 2. Complex 1 had an axial bridge of "NH", while 2 had an axial bridge of "N" between the porphyrin and osmium cluster moieties. Complex 1 could be converted to 2 when refluxed in toluene. These two novel porphyrin-osmium clusters are the first axially linked porphyrin-metal cluster complexes. UV/Vis spectroscopy revealed the significant ground state electronic perturbation in the capped complex 2, demonstrating that the remarkable electronic interaction of the moieties within the molecule was achieved by this special structural arrangement. In addition, the electrochemistry of 1 and 2 were investigated and their oxidation current voltage curves are similar to those of indium(III)-porphyrins with a metal-metal sigma bond such as [TPPInRe(CO)(5)] (TPP=tetraphenylporphyrin). The two new molecules also exhibit large nonlinear optical absorption at 532 nm with a ns pulse laser and are potential optical limiting materials for sensor protection in the visible region.

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Electrochemistry and spectroelectrochemistry in indium(III) porphyrins. Reactions of five-coordinate ionic complexes

Cited by 22 publications

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Determinant Role of Electrogenerated Reactive Nucleophilic Species on Selectivity during Reduction of CO₂ Catalyzed by Metalloporphyrins

Determinant Role of Electrogenerated Reactive Nucleophilic Species on Selectivity during Reduction of CO₂ Catalyzed by Metalloporphyrins

Nitrite-sensitive liquid membrane electrodes based on metalloporphyrin derivatives

Synthesis and Nonlinear Optical Absorption of Novel Porphyrin–Osmium‐Cluster Complexes

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Electrochemistry and spectroelectrochemistry in indium(III) porphyrins. Reactions of five-coordinate ionic complexes

Cited by 22 publications

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Determinant Role of Electrogenerated Reactive Nucleophilic Species on Selectivity during Reduction of CO2 Catalyzed by Metalloporphyrins

Determinant Role of Electrogenerated Reactive Nucleophilic Species on Selectivity during Reduction of CO2 Catalyzed by Metalloporphyrins

Nitrite-sensitive liquid membrane electrodes based on metalloporphyrin derivatives

Synthesis and Nonlinear Optical Absorption of Novel Porphyrin–Osmium‐Cluster Complexes

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Product

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Determinant Role of Electrogenerated Reactive Nucleophilic Species on Selectivity during Reduction of CO₂ Catalyzed by Metalloporphyrins

Determinant Role of Electrogenerated Reactive Nucleophilic Species on Selectivity during Reduction of CO₂ Catalyzed by Metalloporphyrins