Spectroelectrochemical behaviour of the trinuclear [Ru3O(O2CCH3)6(isonicotinamide)3] cluster

Toma, Henrique E.; Cunha, Carlos Jorge da

doi:10.1139/v89-250

Cited by 34 publications

(27 citation statements)

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“…A spectroelectrochemical study of [Ru3 (w3 -0 )(a -C H 3 C O O )6 (isonicotinamide)3]'7+ in the Ru3 (II,II,III) state shows a peak at ca. 500 nm with an e of over 1000 dm3 m ol-1 cm-1 [23]. Be cause of the instability of the (II,II,III) species, a spectrum in the near infra-red region was not re ported.…”

Section: Electrochemistry O F the Trirhodium (Iii) And The Triiridiummentioning

confidence: 98%

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Spectroelectrochemical Study of some μ₃-Oxo-μ-acetato Trinuclear Rhodium(III) and Iridium(III) Complexes

Takahashi

Umakoshi

Kikuchi

et al. 1995

Zeitschrift Für Naturforschung B

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New trinuclear rhodium(III) complexes, [Rh3(//3-0)(/i-CH3C00)6(L)3]+ (L = imidazole (Him), 1-methylimidazole (Meim), and 4-methylpyridine (Mepy)) have been prepared. The Him, Meim, and Mepy complexes show reversible one-electron oxidation waves at E1/2 = +1.12, +1.12, and +1.28 V vs Ag/AgCl, respectively, in acetonitrile. Electronic absorption spectra of the one electron oxidized species of these complexes and [Rh3(M3-0)(M-CH3C 0 0 )6(py)3]+ (py = pyridine) (E 1 /2 = +1.32 V ) were obtained by spectroelectrochemical techniques. While the Rh3(III,III,III) states show no strong visible absorption, the Rh3(III,III,IV ) species give a band at ca. 700 nm (e = 3390-5540 mol dm" 3 cm" 1). [Ir3(«3-0)(//-CH3C00)6(py)3]+ with no strong absorption in the visible region, shows two reversible one-electron oxidation waves at +0.68 and +1.86 V in acetonitrile. The electronic absorption spectrum of the one-electron oxidized species (Ir3(III,III,IV )) also shows some absorption bands (688 nm ( e, 5119), 1093 (2325) and 1400 (ca. 1800)). It is suggested that the oxidation removes an electron from the fully occupied anti-bonding orbital based on metal-d7r-/^3-0-pjr interactions, the absorption bands of the (III,III,IV ) species being assigned to transitions to the a«r/-bonding orbital.esting because of their characteristic strong visible absorption and reversible multi-step redox behav iour [2][3][4][5][6][7][8][9][10][11][12][13][14]. It has been suggested that such char acteristic properties are associated with strong intermetallic interactions through the central oxide bridge. The Ru(d^r)-^3 -0 (p jr) interaction is sig nificantly stronger than that of analogous tri nuclear complexes o f first row transition elements. The djr-pjr molecular orbitals shown in Fig. 1 have been proposed for the trinuclear ruthenium complexes [3,15,16], In the study of mixed ruthenium-rhodium complexes, it was suggested that a similar molecular orbital scheme should be appli cable to trirhodium and mixed ruthenium-rhodium complexes [7]. Electronic states o f the oxocentered triiridium (III) complexes [17,18] should also be considered in terms of the djr-pjr molec ular orbital scheme. Thus the oxo-centered tri metal complexes of heavy transition elements could be significantly different from those of first row transition elements with respect to the extent of metal-oxygen-metal interactions. The trinuclear

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Section: Electrochemistry O F the Trirhodium (Iii) And The Triiridiummentioning

confidence: 98%

“…More than ten derivatives of the oxo-carboxylato-triruthenium(III) complexes are available [3,11,13,15,22,23]. X-ray structural determi nations have been reported for some of them [1 1 , 24, 25].…”

Section: Introductionmentioning

confidence: 99%

Spectroelectrochemical Study of some μ₃-Oxo-μ-acetato Trinuclear Rhodium(III) and Iridium(III) Complexes

Takahashi

Umakoshi

Kikuchi

et al. 1995

Zeitschrift Für Naturforschung B

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“…Nos últimos anos, a técnica de espectroscopia vibracional na região do infravermelho tem sido utilizada de forma rotineira na 64 . 17,37,65 . Este processo é reversível e pôde também ser observado quimicamente 2,35 .…”

Section: Esquemaunclassified

Propriedades e aplicações de clusters trinucleares de carboxilatos de rutênio

Alexiou¹,

Dovidauskas²,

Toma³

2000

Quím. Nova

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Recebido em 8/12/99; aceito em 16/3/00 PROPERTIES AND APPLICATIONS OF TRINUCLEAR RUTHENIUM CARBOXYLATE CLUS-TERS. A review with 94 references focusing on µ µ µ µ µ 3 -oxo-triruthenium carboxylate clusters is presented. The electronic, magnetic, electrochemical, and catalytic properties of these compounds are discussed. Main synthetic routes and structural characteristics, including their use as building blocks in supramolecular systems are described.Keywords: ruthenium-acetate clusters; oxo-ruthenium clusters; ruthenium-carboxylated clusters; catalysis. Nas décadas passadas alguns trabalhos de revisão focalizaram a química dos clusters de rutênio [20][21][22][23][24] , e mais recentemente, apenas estudos mais específicos tem sido publicados [25][26][27] . O objetivo deste trabalho é apresentar uma visão abrangente da química destes compostos, considerando que a maioria dos trabalhos foram feitos nos anos 90 e que os aspectos recentes, mais relevantes, não foram ainda apresentados. REVISÃO INTRODUÇÃO ASPECTOS SINTÉTICOSNesse ítem, descrevemos a síntese dos clusters simétricos

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“…99,100 The active species consist of high-valence metal-oxo porphyrins, which are very reactive and sensitive to substituent effects at the meso-aryl and β-pyrrol carbon atoms. The binding of selected metal complexes [101][102][103] such as the trinuclear µ 3 -oxo-ruthenium acetate clusters 24,[104][105][106][107][108][109][110] to the periphery of the metalloporphyrin ring provides an interesting strategy 111 to improve the activity of the porphyrin catalyst, as in the MnTCP species 112 (Figure 16), as a consequence of their electron withdrawing/donor and/or electron transfer properties, or by acting as cofactors, or by creating new pathways for the oxidation of organic substrates.…”

Section: Oxidative Catalysis and Cytochrome P-450 Activitymentioning

confidence: 99%

Molecular Materials and Devices: Developing New Functional Systems Based on the Coordination Chemistry Approach

Toma

2004

ChemInform

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Neste limiar da era nanotecnológica, o planejamento molecular dos materiais e os estudos de moléculas isoladas estão abrindo imensas possibilidades no emprego de sistemas moleculares em dispositivos eletrônicos e fotônicos, bem como em aplicações tecnológicas baseadas em propriedades de chaveamento ou reconhecimento molecular. Com esse escopo, os químicos inorgânicos em particular, podem aplicar com vantagens as estratégias proporcionadas pela química de coordenação, para construir nanomateriais funcionais que permitam a exploração das propriedades dos centros metálicos e das características dos ligantes presentes. A química de coordenação também oferece recursos eficientes na auto-montagem de nanoestruturas, baseadas na especificidade da interação metal-ligante e nas características estereoquímicas dos complexos. Diversos materiais moleculares gerados a partir de compostos inorgânicos e metal-orgânicos são focalizados neste artigo, com ênfase em novas porfirinas e porfirazinas supramoleculares, clusters e complexos metálicos. Tais sistemas também são enfocados sob o ponto de vista de suas aplicações em catálise, sensores e dispositivos moleculares.At the onset of the nanotechnology age, molecular designing of materials and single molecule studies are opening wide possibilities of using molecular systems in electronic and photonic devices, as well as in technological applications based on molecular switching or molecular recognition. In this sense, inorganic chemists are privileged by the possibility of using the basic strategies of coordination chemistry to build up functional supramolecular materials, conveying the remarkable chemical properties of the metal centers and the characteristics of the ancillary ligands. Coordination chemistry also provides effective self-assembly strategies based on specific metal-ligand affinity and stereochemistry. Several molecular based materials, derived from inorganic and metal-organic compounds are focused on this article, with emphasis on new supramolecular porphyrins and porphyrazines, metal-clusters and metal-polyimine complexes. Such systems are also discussed in terms of their applications in catalysis, sensors and molecular devices.

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Spectroelectrochemical behaviour of the trinuclear [Ru₃O(O₂CCH₃)₆(isonicotinamide)₃] cluster

Cited by 34 publications

References 1 publication

Spectroelectrochemical Study of some μ₃-Oxo-μ-acetato Trinuclear Rhodium(III) and Iridium(III) Complexes

Spectroelectrochemical Study of some μ₃-Oxo-μ-acetato Trinuclear Rhodium(III) and Iridium(III) Complexes

Propriedades e aplicações de clusters trinucleares de carboxilatos de rutênio

Molecular Materials and Devices: Developing New Functional Systems Based on the Coordination Chemistry Approach

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Spectroelectrochemical behaviour of the trinuclear [Ru3O(O2CCH3)6(isonicotinamide)3] cluster

Cited by 34 publications

References 1 publication

Spectroelectrochemical Study of some μ3-Oxo-μ-acetato Trinuclear Rhodium(III) and Iridium(III) Complexes

Spectroelectrochemical Study of some μ3-Oxo-μ-acetato Trinuclear Rhodium(III) and Iridium(III) Complexes

Propriedades e aplicações de clusters trinucleares de carboxilatos de rutênio

Molecular Materials and Devices: Developing New Functional Systems Based on the Coordination Chemistry Approach

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Product

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Spectroelectrochemical behaviour of the trinuclear [Ru₃O(O₂CCH₃)₆(isonicotinamide)₃] cluster

Spectroelectrochemical Study of some μ₃-Oxo-μ-acetato Trinuclear Rhodium(III) and Iridium(III) Complexes

Spectroelectrochemical Study of some μ₃-Oxo-μ-acetato Trinuclear Rhodium(III) and Iridium(III) Complexes