Metalloprotein electron-transfer mechanisms. Quenching of electronically excited tris(2,2'-bipyridine)ruthenium(II) by reduced blue copper proteins

English, Ann M.; DeLaive, Patricia J.; Gray, Harry B.; Lum, Vanessa

doi:10.1021/ja00367a047

Cited by 14 publications

(13 citation statements)

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“…Yield: 0.088 g (62%). 1 In the dark, to a Schlenk flask equipped with a stir bar was added 9,9'-dimethyl-4,5-diazafluorene (0.0749 g, 0.364 mmol) and 50 mL of diethyl ether. Then Mn(CO) 5 Br (0.1000g, 0.382 mmol) was added and the reaction was brought to reflux.…”

Section: Preparation Of Mn(co) 3 (45-diazafluorene)br (2)mentioning

confidence: 99%

“…Yield: 0.1098 g (73%). 1 In the dark, to a three-neck round bottom flask equipped with a stir bar was added 9,9'-dimethyl-4,5-diazafluorene (0.1000 g, 0.509 mmol), RuCl 3 × H 2 O (0.0266 g, 0.128 mmol), and Zn 0 powder (0.0420 g, 0.642 mmol). A 2:1 ethanol:water mixture was used as a solvent to suspend the material, the reaction mixture was brought to reflux, and was allowed to stir overnight.…”

Section: Preparation Of Mn(co) 3 (45-diazafluorene)br (2)mentioning

confidence: 99%

“…Ligands based upon 4,5-diazafluorene (daf) have several features in common with the workhorse R bpy ligands, and thus offer a notable alternative for development of new metal complexes and catalysts [1]. In particular, both daf and bpy have 12e − π systems and both commonly bind to metals in a κ 2 fashion.…”

Section: Introductionmentioning

confidence: 99%

“…Here, we now report the synthesis, characterization, and electrochemical properties of Mn(CO) 3 Br(daf) (2), Mn(CO) 3 Br(Me 2 daf) (3), and [Ru(Me 2 daf) 3 ](PF 6 ) 2 (5), and compare their properties to the more common analogues Mn(CO) 3 (bpy)Br (1) and [Ru(bpy) 3 ] 2+ (4), respectively (see Chart 1 for structures of all compounds). We find that the use of daf and Me 2 daf ligands in the complexes leads to unique spectroscopic features in the NMR and electronic absorption spectra, as well as a characteristic shift in the C-O vibrational frequencies found in the infrared (IR) spectra of 2 and 3 compared to that of 1.…”

Section: Introductionmentioning

confidence: 99%

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4,5-Diazafluorene and 9,9’-Dimethyl-4,5-Diazafluorene as Ligands Supporting Redox-Active Mn and Ru Complexes

et al. 2020

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4,5-diazafluorene (daf) and 9,9’-dimethyl-4,5-diazafluorene (Me2daf) are structurally similar to the important ligand 2,2’-bipyridine (bpy), but significantly less is known about the redox and spectroscopic properties of metal complexes containing Me2daf as a ligand than those containing bpy. New complexes Mn(CO)3Br(daf) (2), Mn(CO)3Br(Me2daf) (3), and [Ru(Me2daf)3](PF6)2 (5) have been prepared and fully characterized to understand the influence of the Me2daf framework on their chemical and electrochemical properties. Structural data for 2, 3, and 5 from single-crystal X-ray diffraction analysis reveal a distinctive widening of the daf and Me2daf chelate angles in comparison to the analogous Mn(CO)3(bpy)Br (1) and [Ru(bpy)3]2+ (4) complexes. Electronic absorption data for these complexes confirm the electronic similarity of daf, Me2daf, and bpy, as spectra are dominated in each case by metal-to-ligand charge transfer bands in the visible region. However, the electrochemical properties of 2, 3, and 5 reveal that the redox-active Me2daf framework in 3 and 5 undergoes reduction at a slightly more negative potential than that of bpy in 1 and 4. Taken together, the results indicate that Me2daf could be useful for preparation of a variety of new redox-active compounds, as it retains the useful redox-active nature of bpy but lacks the acidic, benzylic C–H bonds that can induce secondary reactivity in complexes bearing daf.

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Section: Preparation Of Mn(co) 3 (45-diazafluorene)br (2)mentioning

confidence: 99%

Section: Preparation Of Mn(co) 3 (45-diazafluorene)br (2)mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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4,5-Diazafluorene and 9,9’-Dimethyl-4,5-Diazafluorene as Ligands Supporting Redox-Active Mn and Ru Complexes

et al. 2020

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“…For example, quenching of the luminescent excited state of tris-(2,2'-bipyridine)ruthenium(II) by electron transfer from several reduced type I copper proteins (e.g. azurin, stellacyanin and plastocyanin) has been observed (English et al, 1982).…”

Section: Introductionmentioning

confidence: 99%

PHOTO‐INDUCED ELECTRON EJECTION FROM THE REDUCED COPPER OF Pseudomonas aeruginosa AZURIN

Corin¹,

Gould

1989

Photochem & Photobiology

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The reduced form of Pseudomonas aeruginosa azurin exhibits an enhanced absorbance in the UV compared to that of the oxidized protein. This enhancement has also been observed for azurins from other bacterial species and for another type I copper protein, plastocyanin. Pulsed laser excitation of the reduced azurin in the region of enhanced absorbance at 308 nm results in single photon, rapid (less than 30 ns) oxidation of the copper center and formation of the hydrated electron with a quantum yield of 0.05. The hydrated electron reacts in the expected manner with scavengers such as nitrous oxide, oxygen, acetone and nitromethane. In the absence of scavengers, the electron reacts with the protein, including the disulfide bond, to form the disulfide radical anion, observed at 410 nm. The overall photophysical event involves a charge-transfer to solvent transition although the existence of intermediate states can not be excluded.

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ChemInform Abstract: Metalloprotein Electron‐Transfer Mechanisms. Quenching of Electronically Excited Tris(2,2′‐bipyridine)ruthenium(II) by Reduced Blue Copper Proteins (Azurin, Plastocyanin und Stellacyanin).

English¹,

Lum²,

DeLaive³

et al. 1982

Chemischer Informationsdienst

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Metalloprotein electron-transfer mechanisms. Quenching of electronically excited tris(2,2'-bipyridine)ruthenium(II) by reduced blue copper proteins

Cited by 14 publications

References 1 publication

4,5-Diazafluorene and 9,9’-Dimethyl-4,5-Diazafluorene as Ligands Supporting Redox-Active Mn and Ru Complexes

4,5-Diazafluorene and 9,9’-Dimethyl-4,5-Diazafluorene as Ligands Supporting Redox-Active Mn and Ru Complexes

PHOTO‐INDUCED ELECTRON EJECTION FROM THE REDUCED COPPER OF Pseudomonas aeruginosa AZURIN

ChemInform Abstract: Metalloprotein Electron‐Transfer Mechanisms. Quenching of Electronically Excited Tris(2,2′‐bipyridine)ruthenium(II) by Reduced Blue Copper Proteins (Azurin, Plastocyanin und Stellacyanin).

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