Donor-acceptor electronic coupling as a function of bridging group: mixed-valence diruthenium(II,III) complexes bridged by isonicotinato and isonicotinamido ligands

Chou, Mei H.; Creutz, Carol; Sutin, Norman

doi:10.1021/ic00038a007

Cited by 49 publications

(27 citation statements)

References 6 publications

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“…Correlations have been found between the IVCT solvent shifts and empirical solvent parameters such as the Gutmann donor and acceptor numbers [42]. In studies of dinuclear ruthenium mixed-valence complexes based on -Ru(NH 3 ) 5 , -trans-Ru(NH 3 ) 4 (py) and -Ru(bpy)(NH 3 ) 3 with pyz, 4-cyanopyridine and 4,4 0 -bpy bridging ligands [19,43,44], the IVCT energies correlate linearly with the Gutmann solvent donor number (DN) due to specific H-bonding interactions between the ammine ligands and the solvent molecules. In each case, the magnitude of the specific interaction increased with the donor number of the solvent, and the number of NH 3 ligands in the chromophore.…”

Section: Introductionmentioning

confidence: 99%

Diastereoisomers as probes for solvent reorganizational effects on IVCT in dinuclear ruthenium complexes

D’Alessandro

Keene

2006

Chemical Physics

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Section: Introductionmentioning

confidence: 99%

Diastereoisomers as probes for solvent reorganizational effects on IVCT in dinuclear ruthenium complexes

D’Alessandro

Keene

2006

Chemical Physics

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“…However, the measured value of k h of [(bpy)(CO) 3 Re I (4-CNpy)Ru III (NH 3 ) 5 ] 4þ is still lower (ca. 30 times) than that of [(NH 3 ) 5 Ru III (4-NCpy)Ru III (NH 3 ) 5 ] 6þ [6], as expected from differences in charge and -backbonding effects. Table II shows the value of k h at different temperatures.…”

Section: Resultsmentioning

confidence: 71%

“…In aqueous solutions, S 2 O 2À 8 rapidly oxidizes the ammine ruthenium, as studied previously [5][6][7]. In this work we have investigated (1):…”

Section: Resultsmentioning

confidence: 80%

Nitrile hydrolysis in a rhenium(I)–ruthenium(III) dinuclear complex

Fagalde

Mellace

Katz

et al. 2004

Journal of Coordination Chemistry

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Kinetic data for the hydrolysis reaction: [(CO) 3 (bpy)Re I (4-CNpy)Ru III (NH 3 , that occurs after oxidation with S 2 O 2À 8 of the dinuclear species [(CO) 3 (bpy)Re I (4-CNpy)Ru II (NH 3 ) 5 ] 3þ , have been obtained in aqueous solutions by spectrophotometric techniques. The observed rate constant, k h ¼ (8.6 AE 0.5) Â 10 À3 s À1 , at 25 C, pH ¼ 3.0 (CF 3 COOH) and I ¼ 0.1 M (KCl), is ca. three times higher than the corresponding one for the mononuclear complex [(4-CNpy)Ru III (NH 3 ) 5 ] 3þ , indicating that the catalytic effect of the Ru III (NH 3 ) 5 moiety is enhanced by coordination of the free N of 4-CNpy to the Re I (CO) 3 (bpy) moiety. The value of k h is even higher than that of the dinuclear complex [(trpy)(bpy)Ru II (4-CNpy)Ru III (NH 3 ) 5 ] 5þ (trpy ¼ 2,2 0 :6 0 ,2 00 -terpyridine), reflecting the fact that carbonyls are much stronger -acceptors than polypyridines.

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“…In bis(isonicotinato)iron(II) one inic-ligand is bonded via the pyridine nitrogen atom and the other bridges two metal ions via the carboxylate group, which leads to a three-dimensional polymer [14]. On the other hand, in a mixed-valence diruthenium(II,III) complex isonicotinate acts as a bridging ligand through pyridine nitrogen and carboxylate oxygen atoms [15]. Isonicotinic acid N-oxide with manganesium(II) forms the solid ½MnðH 2 OÞ 6 ½inicNO 2 complex, in which hydrogen bonds between the carboxyl oxygen atoms and two coordinated water molecules have been established [16].…”

Section: Introductionmentioning

confidence: 99%

Chromium(III)-isonicotinate Complexes. Kinetics and Mechanism of Isonicotinate Ligand Liberation in HClO4 Solutions

Szabłowicz

Kita

2006

Transition Met Chem

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Chromium(III)-isonicotinate complexes, cis-½CrðC 2 O 4 Þ 2 (N-inic)ðH 2 OÞ À and ½CrðC 2 O 4 ÞðH 2 OÞ 3 -OH-CrðC 2 O 4 Þ 2 (O-inic) À (N-inic = N-bonded and O-inic = O-bonded isonicotinic acid) were obtained and characterized in solution. Kinetics of acid-catalyzed isonicotinate ligand liberation were studied spectrophotometrically in the 0.1-1.0 M HClO 4 range, at I=1.0 M. The dependencies of the pseudo-first order rate constant on [H + ] were established: k obs ¼ k 0 þ k H Q H ½H þ and k obs ¼ k H Q H ½H þ for the N-inic and O-inic complex, respectively, where k 0 and k H are the rate constants of the spontaneous and the acid-catalyzed reaction paths, and Q H is the protonation constant of the carboxylic group in isonicotinic ligand. The obtained results indicate that N-bonded isonicotinic acid liberation occurs mainly via a spontaneous reaction path and is much slower than O-bonded inic liberation. The mechanisms for these processes are proposed.

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Donor-acceptor electronic coupling as a function of bridging group: mixed-valence diruthenium(II,III) complexes bridged by isonicotinato and isonicotinamido ligands

Cited by 49 publications

References 6 publications

Diastereoisomers as probes for solvent reorganizational effects on IVCT in dinuclear ruthenium complexes

Diastereoisomers as probes for solvent reorganizational effects on IVCT in dinuclear ruthenium complexes

Nitrile hydrolysis in a rhenium(I)–ruthenium(III) dinuclear complex

Chromium(III)-isonicotinate Complexes. Kinetics and Mechanism of Isonicotinate Ligand Liberation in HClO4 Solutions

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