Bis(dioxolene)(bipyridine)ruthenium redox series

Lever, A. B. P.; Auburn, Pamela R.; Dodsworth, Elaine S.; Haga, Masa aki; Liu, Wei; Melnı́k, Milan; Nevin, W. A.

doi:10.1021/ja00232a020

Cited by 126 publications

(67 citation statements)

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“…These data support previous assignments, (6,7) and indeed add useful corroboratory evidence. The contrasting dependencies upon dioxolene and pyridine substituents, arise from changes in the degree of mixing of metal and ligand orbitals due to the symmetry restrictions imposed by the two geometries (7).…”

Section: Synthesis Of the Gis Complexes And Background Literaturesupporting

confidence: 90%

“…The NIR band in the gis-S species shifts slightly to lower energy with more electron donating pyridine 1igand, (Table 1), consistent with the MLCT Ru d ---> semiquinone (7t*) transition, previouI' assigned in the spectra of the analogous bipyridine species (6). The lower energy of tho, ".j d in the pyridine series, relative to the bipyridine series, arises from the greater stabilisation of the d orbitals by the bipyridine ligand.…”

Section: Synthesis Of the Gis Complexes And Background Literaturesupporting

confidence: 68%

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The Trans-Cis Isomerisation of Bis(dioxolene)bis(pyridine)Ruthenium Complexes

Tse¹,

Auburn²,

Lever³

1992

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Section: Synthesis Of the Gis Complexes And Background Literaturesupporting

confidence: 90%

Section: Synthesis Of the Gis Complexes And Background Literaturesupporting

confidence: 68%

The Trans-Cis Isomerisation of Bis(dioxolene)bis(pyridine)Ruthenium Complexes

Tse¹,

Auburn²,

Lever³

1992

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“…3). Since the ruthenium ion is in the q4 oxidation state in the complexes, the bands may therefore be assigned as ligand to metal charge-transfer transitions from sulfur to the metal ion [48][49][50][51][52]. The direct comparisons of the solid state reflectance spectra of 1 with the solution absorption spectra (Fig.…”

Section: Solution Properties Of the Complexesmentioning

confidence: 99%

Ruthenium dithiophosphates: synthesis, X-ray crystal structure, spectroscopic and electrochemical properties

et al. 2000

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The reactions of ammonium salts of dialkyldithiophosphate ligands, (RO) 2 PS 2 y NH 4 q (RsMe/Et), with Ru III Cl 3 P3H 2 O in methanol solvent and under N 2 atmosphere result in one-electron paramagnetic tris complexes {(RO) 2 PS 2 } 3 Ru III (1) in the solid state. The molecular structures of both complexes were determined by single-crystal X-ray diffraction. This shows the expected pseudo-octahedral geometry with reasonable strain due to the presence of a four-membered chelate ring. The reflectance spectra of the solid complexes display two bands in the range 596-476 nm and in the solid state the complexes exhibit one isotropic EPR signal at 77 K. Although the complexes 1 are stable in the solid state, in solution the complexes are transformed selectively into the diamagnetic and electrically non-conducting sulfur-bridged dimetallic species [{(RO) 2 PS 2 } 2 Ru IV (m-S) 2 Ru IV {S 2 P(OR) 2 } 2 ]. The formation of dimeric species in the solution state is authenticated by the electrospray mass spectrum of one representative complex where RsEt (1b). In dichloromethane solution the complexes show two moderately strong sulfur to ruthenium charge-transfer transitions in the range 514-419 nm, and two strong ligand based transitions in the UV region. The complexes exhibit two successive reversible reductions in the ranges 1.01™0.91 V and y0.44™y0.49 V versus SCE corresponding to Ru IV -Ru IV /Ru III -Ru III and Ru III -Ru III /Ru II -Ru II couples respectively. Electrochemically or chemically generated first step reduced complexes [{(RO) 2 PS 2 } 2 Ru III (m-S) 2 Ru III {S 2 P(OR) 2 } 2 ] 2y display two ligand to metal charge-transfer transitions in the visible region and in the complexes the two one-electron paramagnetic metal centers (low-spin Ru III , ,Ss1/2)are antiferromagnetically coupled. t 2gThe second step reduced species [{(RO) 2 PS 2 } 2 Ru II (m-S) 2 Ru II {S 2 P(OR) 2 } 2 ] 4y are observed to be very unstable.

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“…Where more than one r-accepting ligand is present, such as in the series [Ru(dppm),(CO)XI+ and [~u(bpy)(dppe)(CO)XI+ (X = C1, Br, I) (16), the trans isomer is more difficult to oxidise by up to 450 mV. In our dioxolene system, cou le V (Table 3) R is most closely associated with the RU"'/RU couple (6,7). The lack of any shift in this couple between cis and trans isomer arises because at this oxidation level the RU' is bound to the non-r-accepting catechol.…”

Section: Electrochemistrymentioning

confidence: 82%

“…Assignments have been discussed in depth previously (6,7). Arguments have been expressed in the literature relating differences in the electrochemical behaviour of cis and trans pairs to differences in electronic structure.…”

Section: Electrochemistrymentioning

confidence: 99%

The trans–cis isomerisation of bis(dioxolene)bis(pyridine) ruthenium complexes

Tse¹,

Auburn²,

Lever³

1992

Can. J. Chem.

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Yu-HONG TSE, PAMELA R. AUBURN, and A. B. P. LEVER. Can. J. Chem. 70, 1849 (1992). The isomerisation of trans to cis bis(3,5-di-t-butylbenzosemiquinonato)bis(R-pyndine)ruthenium, Ru(RPy),(DTBDiox),, is induced by warming with an excess of R-pyridine, where R = 3-chloro, 4-methyl, 4-phenyl, or 4-butyl. The rates of these reactions, for the species with R-Py = 3-chloropyridine, were monitored in o-dichlorobenzene [Traduit par la redaction]

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Bis(dioxolene)(bipyridine)ruthenium redox series

Cited by 126 publications

References 0 publications

The Trans-Cis Isomerisation of Bis(dioxolene)bis(pyridine)Ruthenium Complexes

The Trans-Cis Isomerisation of Bis(dioxolene)bis(pyridine)Ruthenium Complexes

Ruthenium dithiophosphates: synthesis, X-ray crystal structure, spectroscopic and electrochemical properties

The trans–cis isomerisation of bis(dioxolene)bis(pyridine) ruthenium complexes

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