Electronic structure and redox properties of the clusters [Ru3O(CH3CO2)6L3]n+

Baumann, John A.; Salmon, Dennis J.; Wilson, Stephen T.; Meyer, Thomas J.; Hatfield, William E.

doi:10.1021/ic50190a007

Cited by 213 publications

(303 citation statements)

References 13 publications

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“…The [R~~0(00CCH~)~(isonic)~]A (A = PF6-or BFC) cluster was synthesized according to the procedure previously reported in the literature for the 2-methyl pyrazine analogue (4). Anal.…”

Section: Methodsmentioning

confidence: 99%

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

Toma¹,

Cunha²

1989

Can. J. Chem.

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. Can. J. Chem. 67, 1632 (1989).The [R~~0(00CCH~)~(isonicotinarnide)~] cluster exhibits reversible electrochemical and spectroelectrochemical behaviour in acetonitrile solutions, associated with a series of successive p-0x0 ~u '~~u '~~u~~~/~u~~~u '~~~u " ' / .../RU"RU"RU" redox couples with E? = 2.16, 1.21, 0.19, -0.98, and -1.4 V versus SHE. The metal-isonicotinamide and metal-metal chargetransfer transitions shift to lower energies as the oxidation states of the ruthenium ions decrease. In alkaline aqueous solution, the p-0x0 R u " '~u~~' R u~~ cluster can be reversibly reduced to the p-0x0 RU"'RU"RU"product (E? = -0.85 V); however, below pH 4, the reduction proceeds according to two successive steps, yielding R u "~u~~R u " species with loss of the central oxygen ion. These species can be reoxidized in the reverse potential scan, regenerating the p-0x0 RU"'RU"'RU" complex.

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“…The [R~~0(00CCH~)~(isonic)~]A (A = PF6-or BFC) cluster was synthesized according to the procedure previously reported in the literature for the 2-methyl pyrazine analogue (4). Anal.…”

Section: Methodsmentioning

confidence: 99%

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

Toma¹,

Cunha²

1989

Can. J. Chem.

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“…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%

“…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.…”

mentioning

confidence: 99%

“…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.…”

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confidence: 99%

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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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“…23 [Ru 3 O(OAc) 6 (py) 2 (CH 3 OH)]PF 6 was prepared by adapting the four steps procedure previously reported in the literature. 24 The initial step involves the synthesis of the [Ru 3 O(OAc) 6 2 O were dissolved in a mixture of 120 mL of dry ethanol and 28 mL of acetic acid in a round bottomed flask (500 mL) and 10.2 g of NaOAc.3H 2 O were added in small portions. The mixture was kept under reflux for 4 h and allowed to under rest overnight.…”

Section: Materials and Instrumentationmentioning

confidence: 99%

Electrocatalytic oxidation of methanol by the [Ru3O(OAc)6(py)2(CH3OH)]3+cluster: improving the metal-ligand electron transfer by accessing the higher oxidation states of a multicentered system

et al. 2010

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Recebido em 24/5/10; aceito em 27/7/10; publicado na web em 15/10/10 /Ru 3 IV,III,III successive redox couples, respectively. Above 1.7 V, formation of two Ru IV centers enhances the 2-electron oxidation of the methanol ligand yielding formaldehyde, in agreement with the theoretical evolution of the HOMO levels as a function of the oxidation states. This work illustrates an important strategy to improve the efficiency of the oxidation catalysis, by using a multicentered redox catalyst and accessing its multiple higher oxidation states.

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Electronic structure and redox properties of the clusters [Ru3O(CH3CO2)6L3]n+

Cited by 213 publications

References 13 publications

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

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

Electrocatalytic oxidation of methanol by the [Ru3O(OAc)6(py)2(CH3OH)]3+cluster: improving the metal-ligand electron transfer by accessing the higher oxidation states of a multicentered system

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Electronic structure and redox properties of the clusters [Ru3O(CH3CO2)6L3]n+

Cited by 213 publications

References 13 publications

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

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

Electrocatalytic oxidation of methanol by the [Ru3O(OAc)6(py)2(CH3OH)]3+cluster: improving the metal-ligand electron transfer by accessing the higher oxidation states of a multicentered system

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

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