Tris(bipyridine)ruthenium(II) chloride

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Tris(bipyridine)ruthenium(II) chloride
Tris(bipyridine)ruthenium(II) chloride.png
Tris(bipyridine)ruthenium(II)-chloride-powder.jpg
Names
Other names
Ru-bpy
Ruthenium-tris(2,2’-bipyridyl) dichloride
Identifiers
ECHA InfoCard 100.034.772
RTECS number VM2730000
Properties
C30H24N6Cl2Ru·6H2O
Molar mass 640.53 g/mol (anhydrous)
748.62 g/mol (hexahydrate)
Appearance red solid
Density solid
Melting point >300 °C
slightly soluble in water; soluble in acetone
Structure
Octahedral
0 D
Hazards
Main hazards mildly toxic
R-phrases (outdated) none
S-phrases (outdated) S22 S24/25
Related compounds
Related compounds
Ruthenium trichloride
2,2'-bipyridine
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Tris(bipyridine)ruthenium(II) chloride is the coordination compound with the formula [Ru(bpy)3]Cl2. This red crystalline salt is obtained as the hexahydrate, although all of the properties of interest are in the cation [Ru(bpy)3]2+, which has received much attention because of its distinctive optical properties. The chlorides can be replaced with other anions, such as PF6.

Synthesis and structure[edit]

Structure of [Ru(bpy)3]2+

This salt is prepared by treating an aqueous solution of ruthenium trichloride with 2,2'-bipyridine. In this conversion, Ru(III) is reduced to Ru(II), and hypophosphorous acid is typically added as a reducing agent.[1]

[Ru(bpy)3]2+ is an octahedral coordination complex containing a central low spin d6 Ru(II) ion and three bidentate bpy ligands. The complex is chiral, with D3 symmetry. It has been resolved into its enantiomers, which are kinetically stable. In its lowest lying triplet excited state the molecule is thought to attain lower C2 symmetry, as the excited electron is localized primarily on a single bipyridyl ligand.[2][3]

Photochemistry of [Ru(bpy)3]2+[edit]

Transitions of [Ru(bpy)3]2+

[Ru(bpy)3]2+ absorbs ultraviolet and visible light. Aqueous solutions of [Ru(bpy)3]Cl2 are orange due to a strong MLCT absorption at 452 ± 3 nm (extinction coefficient of 14,600 M−1cm−1). Further absorption bands are found at 285 nm corresponding to ligand centered π*← π transitions and a weak transition around 350 nm (d-d transition).[4] ligh absorption results in formation of an excited state have a relatively long lifetime of 890 ns in acetonitrile[5] and 650 ns in water.[5] The excited state relaxes to the ground state by emission of a photon or non-radiative relaxation. The quantum yield is 2.8% in air-saturated water at 298K and the emission maximum wavelength is 620 nm.[6] The long lifetime of the excited state is attributed to the fact that it is triplet, whereas the ground state is a singlet state and in part due to the fact that the structure of the molecule allows for charge separation. Singlet-triplet transitions are forbidden and therefore often slow.

Like all molecular excited states, the triplet excited state of [Ru(bpy)3]2+ has both stronger oxidizing and reducing properties than its ground state. This situation arises because the excited state can be described as an Ru3+ complex containing a bpy·− radical anion as a ligand. Thus, the photochemical properties of [Ru(bpy)3]2+ are reminiscent of the photosynthetic assembly, which also involves separation of an electron and a hole.[7]

[Ru(bpy)3]2+ has been examined as a photosensitizer for both the oxidation and reduction of water. Upon absorbing a photon, [Ru(bpy)3]2+ converts to the aforementioned triplet state, denoted [Ru(bpy)3]2+*. This species transfers an electron, located on one bpy ligand, to a sacrificial oxidant such as peroxodisulfate (S2O82−). The resulting [Ru(bpy)3]3+ is a powerful oxidant and oxidizes water into O2 and protons via a metal oxide catalyst.[8] Alternatively, the reducing power of [Ru(bpy)3]2+* can be harnessed to reduce methylviologen, a recyclable carrier of electrons, which in turn reduces protons at a platinum catalyst. For this process to be catalytic, a sacrificial reductant, such as EDTA4− or triethanolamine is provided to return the Ru(III) back to Ru(II).

Derivatives of [Ru(bpy)3]2+ are numerous.[9][10] Such complexes are widely discussed for applications in biodiagnostics, photovoltaics and organic light-emitting diode, but no derivative has been commercialized. Application of [Ru(bpy)3]2+ and its derivatives to fabrication of optical chemical sensors is arguably one of the most successful areas so far.[11]

[Ru(bpy)3]2+ and photoredox catalysis[edit]

Photoredox catalysis using combination of [Ru(bpy)3]2+ catalyst and visible light has been considered as a tool for preparative organic chemistry since the 1970s.[12] However, only a few research groups dealt with this topic until the beginning of the 21st century. Since 2008, development of this bond-forming strategy for organic synthesis has gained considerable momentum due to the seminal studies by MacMillan,[13] Yoon,[14] and Stephenson[15] groups. Depending on the choice of suitable reductive or oxidative quencher, the [Ru(bpy)3]2+ catalyst can be used to trigger photoreduction or photooxidation, respectively. Current status of this field has been recently summarized in several review articles.[12][16][17][18] It can be anticipated that photoredox reactivity of complexes based on metals other than Ru (e.g. Ir, Re, and bimetallic photocatalysts) will also be intensively explored. Additionally, transformations triggered by purely organic photoredox catalysts is also possible.[19]

Safety[edit]

Metal bipyridine as well as related phenanthroline complexes are generally bioactive, as they can act as intercalating agents.

References[edit]

  1. ^ Broomhead J. A.; Young C. G. (1990). Tris(2,2'-bipyridine)Ruthenium(II) Dichloride Hexahydrate. Inorganic Syntheses. 28. pp. 338–340. doi:10.1002/9780470132593.ch86. ISBN 9780470132593.
  2. ^ Yeh, Alvin T.; Charles V. Shank; James K. McCusker (2000). "Ultrafast Electron Localization Dynamics Following Photo-Induced Charge Transfer". Science. 289 (5481): 935–938. CiteSeerX 10.1.1.612.8363. doi:10.1126/science.289.5481.935. PMID 10937993. Retrieved 19 February 2014.
  3. ^ Thompson, David W.; Ito, Akitaka; Meyer, Thomas J. (30 June 2013). "[Ru(bpy)3]2+* and other remarkable metal-to-ligand charge transfer (MLCT) excited states". Pure and Applied Chemistry. 85 (7): 1257–1305. doi:10.1351/PAC-CON-13-03-04.
  4. ^ Kalyanasundaram, K. (1982). "Photophysics, photochemistry and solar energy conversion with tris(bipyridyl)ruthenium(II) and its analogues". Coordination Chemistry Reviews. 46: 159–244. doi:10.1016/0010-8545(82)85003-0. Retrieved 19 February 2014.
  5. ^ a b Montalti, Marco; Alberto Cedi; Luca Prodi; M. Teresa Gandolfi (2006). Handbook of Photochemistry (3rd ed.). 6000 Broken Sound Prkway NW, Suite 200 Boca Raton, FL: CRC press Taylor & Francis Group. pp. 379–404. ISBN 978-0-8247-2377-4.
  6. ^ Nakamaru, Katsumi (1982). "Synthesis, luminescence quantum yields, and lifetimes of trischelated ruthenium(II) mixed-ligand complexes including 3,3'-dimethy1-2,2'-bipyridyl". Bulletin of the Chemical Society of Japan. 55: 2697.
  7. ^ A. J. Bard & M. A. Fox (1995). "Artificial Photosynthesis: Solar Splitting of Water to Hydrogen and Oxygen". Acc. Chem. Res. 28 (3): 141–145. doi:10.1021/ar00051a007.
  8. ^ M. Hara; C. C. Waraksa; J. T. Lean; B. A. Lewis & T. E. Mallouk (2000). "Photocatalytic Water Oxidation in a Buffered Tris(2,2'-bipyridyl)ruthenium Complex-Colloidal IrO2 System". J. Phys. Chem. A. 104 (22): 5275–5280. CiteSeerX 10.1.1.547.1886. doi:10.1021/jp000321x.
  9. ^ A. Juris; V. Balzani; F. Barigelletti; S. Campagna; P. Belser & A. von Zelewsky (1988). "Ru(II) polypyridine complexes - photophysics, photochemistry, electrochemistry, and chemiluminescence". Coord. Chem. Rev. 84: 85–277. doi:10.1016/0010-8545(88)80032-8.
  10. ^ S. Campagna; F. Puntoriero; F. Nastasi; G. Bergamini & V. Balzani (2007). Photochemistry and photophysics of coordination compounds: ruthenium. Top. Curr. Chem. Topics in Current Chemistry. 280. pp. 117–214. doi:10.1007/128_2007_133. ISBN 978-3-540-73346-1.
  11. ^ G. Orellana & D. Garcia-Fresnadillo (2004). Environmental and Industrial Optosensing with Tailored Luminescent Ru(II) Polypyridyl Complexes. Springer Ser. Chem. Sens. Biosens. 1. pp. 309–357. doi:10.1007/978-3-662-09111-1_13. ISBN 978-3-642-07421-9.
  12. ^ a b F. Teply (2011). "Photoredox catalysis by [Ru(bpy)3]2+ to trigger transformations of organic molecules. Organic synthesis using visible-light photocatalysis and its 20th century roots". Collect. Czech. Chem. Commun. 76 (7): 859–917. doi:10.1135/cccc2011078.
  13. ^ D. A. Nicewicz; D. W. C. MacMillan (2008). "Merging photoredox catalysis with organocatalysis: The direct asymmetric alkylation of aldehydes". Science. 322 (5898): 77–80. doi:10.1126/science.1161976. PMC 2723798. PMID 18772399.
  14. ^ M. A. Ischay; M. E. Anzovino; J. Du; T. P. Yoon (2008). "Efficient visible light photocatalysis of [2+2] enone cycloadditions". J. Am. Chem. Soc. 130 (39): 12886–12887. doi:10.1021/ja805387f. PMID 18767798.
  15. ^ J. M. R. Narayanam; J. W. Tucker; C. R. J. Stephenson (2009). "Electron-transfer photoredox catalysis: Development of a tin-free reductive dehalogenation reaction". J. Am. Chem. Soc. 131 (25): 8756–8757. doi:10.1021/ja9033582. PMID 19552447.
  16. ^ J. M. R. Narayanam; C. R. J. Stephenson (2011). "Visible light photoredox catalysis: applications in organic synthesis". Chem. Soc. Rev. 40 (1): 102–113. doi:10.1039/b913880n. PMID 20532341.
  17. ^ T. P. Yoon; M. A. Ischay; J. Du (2010). "Visible light photocatalysis as a greener approach to photochemical synthesis". Nat. Chem. 2 (7): 527–532. doi:10.1038/nchem.687. PMID 20571569.
  18. ^ K. Zeitler (2009). "Photoredox catalysis with visible light". Angew. Chem. Int. Ed. 48 (52): 9785–9789. doi:10.1002/anie.200904056. PMID 19946918.
  19. ^ Romero, Nathan A.; Nicewicz, David A. (10 June 2016). "Organic Photoredox Catalysis". Chemical Reviews. 116 (17): 10075–10166. doi:10.1021/acs.chemrev.6b00057.