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Synthesis, characte...
Synthesis, characterization, and electrochemistry of biorelevant photosensitive low-potential orthometalated ruthenium complexes
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Ryabov, A. D. (författare)
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Le Lagadec, R. (författare)
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Estevez, H. (författare)
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Toscano, R. A. (författare)
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Hernandez, S. (författare)
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Alexandrova, L. (författare)
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Kurova, V. S. (författare)
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- Fischer, Andreas (författare)
- KTH,Oorganisk kemi
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Sirlin, C. (författare)
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Pfeffer, M. (författare)
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(creator_code:org_t)
- 2005-02-10
- 2005
- Engelska.
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 44:5, s. 1626-1634
- Relaterad länk:
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https://urn.kb.se/re...
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https://doi.org/10.1...
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Abstract
Ämnesord
Stäng
- Redox potentials of photosensitive cyclometalated Ru derivatives of 2-phenylpyridine or 2-(4-tolyl)pyridine are controllably decreased by up to 0.8 V within several minutes. This is achieved by irradiation of the ruthena(II)cycles cis-[Ru(o-X-2-py)(LL)(MeCN)(2)]PF6 (2, X = C6H4 (a) or 4-MeC6H3 (b), LL = 1,10-phenanthroline or 2,2'-bipyridine). The cis geometry of the MeCN ligands has been confirmed by the X-ray structural studies. The sigma-bound sp(2) carbon of the metalated ring is trans to LL nitrogen. Complexes 2 are made from [Ru(o-X-2-py)(MeCN)(4)]PF6 (1) and I-L. This trivial ligand substitution is unusual because la reacts readily with phen in MeCN as solvent to give cis-[Ru(o-C6H4-2-py)(phen)(MeCN)(2)]PF6 (2c) in a 83% yield, but bpy does not afford the bpy-containing 2 under the same conditions. cis-[Ru(o-C6H4-2-py)(bpy)(MeCN)(2)]PF6 (2e) has been prepared in CH2Cl2 (74%). Studies of complexes 2c,e by cyclic voltammetry in MeOH in the dark reveal Ru-II/III quasy-reversible redox features at 573 and 578 mV (vs Ag/AgCl), respectively. A minute irradiation 2c and 2e converts them into now species with redox potentials of -230 and 270 mV, respectively. An exceptional potential drop for 2c is accounted for in terms of a photosubstitution of both MeCN ligands by methanol. ESR, H-1 NMR, and UV-vis data indicate that the primary product of photolysis of 2c is an octahedral monomeric low-spin (S = 112) Ru-III species, presumably cis-[Ru-II(o-C6H4-2-py)(phen)(MeOH)2]2+. The primary photoproduct of bpy complex 2e is cis-[Ru-II(O-C6H4-2-py)(bpy)(MeCN)(MeOH)](+), and this accounts for a lower decrease in the redox potential. Irradiation of 2c in the presence of added chloride affords [(phen)(o-C6H4-2-py)(ClRuORuCl)-O-III-Cl-IV(o-C6H4-2-py)(phen)]PF6, a first mu-oxo-bridged mixed valent dimer with a cyclometalated unit. The structure of the dimer has been established by X-ray crystallography.
Nyckelord
- horseradish-peroxidase
- photosubstitution reactions
- cyclometalated complexes
- redox properties
- glucose-oxidase
- water-oxidation
- photochemistry
- biomaterials
- mediators
- catalysis
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Till lärosätets databas
- Av författaren/redakt...
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Ryabov, A. D.
-
Le Lagadec, R.
-
Estevez, H.
-
Toscano, R. A.
-
Hernandez, S.
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Alexandrova, L.
-
visa fler...
-
Kurova, V. S.
-
Fischer, Andreas
-
Sirlin, C.
-
Pfeffer, M.
-
visa färre...
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Inorganic Chemis ...
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