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| 2. |
- Ott, S., et al.
(författare)
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Model of the iron hydrogenase active site covalently linked to a ruthenium photosensitizer : Synthesis and photophysical properties
- 2004
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Ingår i: Inorganic Chemistry. - : American Chemical Society (ACS). - 0020-1669 .- 1520-510X. ; 43:15, s. 4683-4692
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Tidskriftsartikel (refereegranskat)abstract
- A model of the iron hydrogenase active site with the structure [(mu-ADT)Fe-2(CO)(6)] (ADT = azadithiolate (S-CH2-NR-CH2-S), (2: R = 4-bromophenyl, 3: R = 4-iodophenyl)) has been assembled and covalently linked to a [Ru(terpy)(2)](2+) photosensitizer. This trinuclear complex 1 represents one synthetic step toward the realization of our concept of light-driven proton reduction. A rigid phenylacetylene tether has been incorporated as the linking unit in 1 in order to prolong the lifetime of the otherwise short-lived [Ru(terpy)(2)](2+) excited state. The success of this strategy is demonstrated by comparison of the photophysical properties of 1 and of two related ruthenium complexes bearing acetylenic terpyridine ligands, with those of [Ru(terpy)(2)](2+). IR and electrochemical studies reveal that the nitrogen heteroatom of the ADT bridge has a marked influence on the electronic properties of the [Fe-2(CO)(6)] core. Using the Rehm-Weller equation, the driving force for an electron transfer from the photoexcited *[Ru(terpy)(2)](2+) to the diiron site in 1 was calculated to be uphill by 0.59 eV. During the construction of the trinuclear complex 1, n-propylamine has been identified as a decarbonylation agent on the [(mu-ADT)Fe-2(CO)(6)] portion of the supermolecule. Following this procedure, the first azadithiolate-bridged dinuclear iron complex coordinated by a phosphine ligand [(mu-ADT)Fe-2(CO)(5)PPh3] (4, R = 4-bromophenyl) was synthesized.
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| 3. |
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| 4. |
- Salyi, S., et al.
(författare)
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Synthesis of an amino-functionalized model of the Fe-only hydrogenase active site
- 2003
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Ingår i: Chemistry - A European Journal. - : Wiley. - 0947-6539 .- 1521-3765. ; 9:2, s. 557-560
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Tidskriftsartikel (refereegranskat)abstract
- A dinuclear 2Fe2S mimic 6 of the active site of the Fe-only hydrogenases has been synthesized. Complex 6 contains a free amino group which enables linkage to a protein backbone or to a redox active species for the study of electron transfer processes in proteins or in supramolecular systems. The structures of the complex 6 and its Boc-protected precursor 5 could be verified by X-ray crystallography.
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| 5. |
- Schmitt, H., et al.
(författare)
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Synthesis, redox properties, and EPR spectroscopy of manganese(III) complexes of the ligand N,N-bis(2-hydroxybenzyl)-N '-2-hdroxybenzylidene-1,2-diaminoethane : Formation of mononuclear, dinuclear, and even higher nuclearity complexes
- 2002
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Ingår i: Chemistry - A European Journal. - 0947-6539 .- 1521-3765. ; 8:16, s. 3757-3768
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Tidskriftsartikel (refereegranskat)abstract
- The synthesis and characterization of the title trisphenolate ligand are described. From its reaction with manganese(iii) three complexes were isolated. The crystal structures revealed one pentacoordinate monomer and two similar dimers with different solvents of crystallization. In the dimers the metal ions are hexacoordinate and connected through bridging of two phenolates. A combination of electrochemistry and EPR spectroscopy showed that, in acetonitrile, the isolated batches were all identical and mainly monomeric, indicating that the mononuclear complex is in equilibrium with the dimer and perhaps also with complexes of higher nuclearity, as suggested by the detection of both the trimer and the tetramer by electrospray ionization mass spectrometry (ESI-MS). The successful use of the monomer batch as an epoxidation catalyst indicated that a high-valent manganese-oxo species can be formed, although it is probably short-lived. This is also suggested by EPR studies of the species formed by electrochemical oxidation of the complex. Upon one-electron oxidation, a manganese(iv) species was formed, which was at least partly converted to another species containing a phenoxy radical.
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| 6. |
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| 7. |
- Yang, X. C., et al.
(författare)
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Axial ligand exchange reaction on ruthenium phthalocyanines
- 2005
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Ingår i: Journal of Porphyrins and Phthalocyanines. - 1088-4246 .- 1099-1409. ; 9:4, s. 248-255
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Tidskriftsartikel (refereegranskat)abstract
- Bis(4-methylpyridine)phthalocyaninato ruthenium(II) has been synthesized. It was proved by single-crystal X-ray diffraction that the central Ru(II) atom is bonded to six N atoms in an elongated octahedral configuration, and the axial ligands have a significantly longer Ru-N bond distance, 2.101(4) angstrom, than the independent pyrrol Ru-N bond, 1.99 angstrom. Therefore, the axial ligands can be exchanged by other ligands. The ligand exchange reactions with diethyl pyridyl-4-phosphonate and diethyl pyridylmethyl-4-phosphonate were studied in high boiling-point solvents at elevated temperatures, ca 160 degrees C. Mono-ligand as well as double-ligand replaced complexes were obtained. The complexes have been isolated by column chromatography. These complexes have potential applications, such as in dye sensitized solar cells.
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