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
Delta-ruthenium-tris(bipyridine)-cation-3D-balls.png
Names
Other names
Ru-bpy
Ruthenium-tris(2,2’-bipyridyl) dichloride
Identifiers
3D model (JSmol)
ECHA InfoCard 100.034.772 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • (anhydrous):238-266-7
PubChem CID
RTECS number
  • (anhydrous):VM2730000
UNII
  • (anhydrous):InChI=1S/3C10H8N2.2ClH.Ru/c3*1-3-7-11-9(5-1)10-6-2-4-8-12-10;;;/h3*1-8H;2*1H;/q;;;;;+2/p-2
    Key: SJFYGUKHUNLZTK-UHFFFAOYSA-L
  • (hexahydrate):InChI=1S/3C12H8N2.2ClH.6H2O.Ru/c3*1-3-9-5-6-10-4-2-8-14-12(10)11(9)13-7-1;;;;;;;;;/h3*1-8H;2*1H;6*1H2;/q;;;;;;;;;;;+2/p-2
    Key: UUSPGQXHSZVVNL-UHFFFAOYSA-L
  • (anhydrous):C1=CC=NC(=C1)C2=CC=CC=N2.C1=CC=NC(=C1)C2=CC=CC=N2.C1=CC=NC(=C1)C2=CC=CC=N2.Cl[Ru]Cl
  • (hexahydrate):C1=CC2=C(C3=C(C=CC=N3)C=C2)N=C1.C1=CC2=C(C3=C(C=CC=N3)C=C2)N=C1.C1=CC2=C(C3=C(C=CC=N3)C=C2)N=C1.O.O.O.O.O.O.[Cl-].[Cl-].[Ru+2]
Properties
C30H24N6Cl2Ru·6H2O
Molar mass 640.53 g/mol (anhydrous)
748.62 g/mol (hexahydrate)
Appearancered solid
Density solid
Melting point >300 °C
slightly soluble in water; soluble in acetone
Structure
Octahedral
0 D
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
mildly toxic
Safety data sheet (SDS) External MSDS
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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Tris(bipyridine)ruthenium(II) chloride is the chloride salt coordination complex with the formula [Ru(bpy)3]Cl2. This polypyridine complex is a red crystalline salt 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.

Contents

Synthesis and structure

cis-Dichlorobis(bipyridine)ruthenium(II) is an intermediate in the synthesis of tris(bipyridine)ruthenium(II) chloride. RuCl2(bipy)2.png
cis-Dichlorobis(bipyridine)ruthenium(II) is an intermediate in the synthesis of tris(bipyridine)ruthenium(II) chloride.

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 octahedral, containing a central low spin d6 Ru(II) ion and three bidentate bpy ligands. The Ru-N distances are 2.053(2), shorter than the Ru-N distances for [Ru(bpy)3]3+. [2] The complex is chiral, with D3 symmetry. It has been resolved into its enantiomers. 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. [3] [4]

Photochemistry of [Ru(bpy)3]2+

Transitions of [Ru(bpy)3] Ruthenium bipyridyl energy level diagram.png
Transitions of [Ru(bpy)3]
Absorption and emission spectrum of [Ru(bpy)3] in alcoholic solution at room temperature Ru(bpy)32+ absorption&emission.png
Absorption and emission spectrum of [Ru(bpy)3] in alcoholic solution at room temperature

[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). [5] Light absorption results in formation of an excited state have a relatively long lifetime of 890 ns in acetonitrile [6] and 650 ns in water. [6] 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 298 K and the emission maximum wavelength is 620 nm. [7] 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. [8]

[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 catalyst. [9] 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 EDTA 4− or triethanolamine is provided to return the Ru(III) back to Ru(II).

Derivatives of [Ru(bpy)3]2+ are numerous. [10] [11] 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. [12]

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

Photoredox catalysis exploits [Ru(bpy)3]2+ as a sensitizer as a strategy for organic synthesis. Many analogues of [Ru(bpy)3]2+ are employed as well. These transformations exploit the redox properties of [Ru(bpy)3]2+* and its reductively quenched derivative [Ru(bpy)3]+. [13] [14] [15] [16]

Safety

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

See also

Related Research Articles

<span class="mw-page-title-main">Polypyridine complex</span>

Polypyridine complexes are coordination complexes containing polypyridine ligands, such as 2,2'-bipyridine, 1,10-phenanthroline, or 2,2';6'2"-terpyridine.

<span class="mw-page-title-main">Bipyridine</span> Group of chemical compounds

Bipyridines are a family of organic compounds with the formula (C5H4N)2, consisting of two pyridyl (C5H4N) rings. Pyridine is an aromatic nitrogen-containing heterocycle. The bipyridines are all colourless solids, which are soluble in organic solvents and slightly soluble in water. Bipyridines, especially the 4,4' isomer, are mainly of significance in pesticides.

<span class="mw-page-title-main">BINAP</span> Chemical compound

BINAP (2,2′-bis(diphenylphosphino)-1,1′-binaphthyl) is an organophosphorus compound. This chiral diphosphine ligand is widely used in asymmetric synthesis. It consists of a pair of 2-diphenylphosphinonaphthyl groups linked at the 1 and 1′ positions. This C2-symmetric framework lacks a stereogenic atom, but has axial chirality due to restricted rotation (atropisomerism). The barrier to racemization is high due to steric hindrance, which limits rotation about the bond linking the naphthyl rings. The dihedral angle between the naphthyl groups is approximately 90°. The natural bite angle is 93°.

<span class="mw-page-title-main">Photosensitizer</span> Type of molecule reacting to light

Photosensitizers are light absorbers that alter the course of a photochemical reaction. They usually are catalysts. They can function by many mechanisms, sometimes they donate an electron to the substrate, sometimes they abstract a hydrogen atom from the substrate. At the end of this process, the photosensitizer returns to its ground state, where it remains chemically intact, poised to absorb more light. One branch of chemistry which frequently utilizes photosensitizers is polymer chemistry, using photosensitizers in reactions such as photopolymerization, photocrosslinking, and photodegradation. Photosensitizers are also used to generate prolonged excited electronic states in organic molecules with uses in photocatalysis, photon upconversion and photodynamic therapy. Generally, photosensitizers absorb electromagnetic radiation consisting of infrared radiation, visible light radiation, and ultraviolet radiation and transfer absorbed energy into neighboring molecules. This absorption of light is made possible by photosensitizers' large de-localized π-systems, which lowers the energy of HOMO and LUMO orbitals to promote photoexcitation. While many photosensitizers are organic or organometallic compounds, there are also examples of using semiconductor quantum dots as photosensitizers.

Organic photochemistry encompasses organic reactions that are induced by the action of light. The absorption of ultraviolet light by organic molecules often leads to reactions. In the earliest days, sunlight was employed, while in more modern times ultraviolet lamps are employed. Organic photochemistry has proven to be a very useful synthetic tool. Complex organic products can be obtained simply.

<span class="mw-page-title-main">2,2′-Bipyridine</span> Chemical compound

2,2′-Bipyridine (bipy or bpy, pronounced ) is an organic compound with the formula C10H8N2. This colorless solid is an important isomer of the bipyridine family. It is a bidentate chelating ligand, forming complexes with many transition metals. Ruthenium and platinum complexes of bipy exhibit intense luminescence, which may have practical applications.

In chemistry, a (redox) non-innocent ligand is a ligand in a metal complex where the oxidation state is not clear. Typically, complexes containing non-innocent ligands are redox active at mild potentials. The concept assumes that redox reactions in metal complexes are either metal or ligand localized, which is a simplification, albeit a useful one.

<span class="mw-page-title-main">Electrochemiluminescence</span> Emission of light from electrochemical reactions

Electrochemiluminescence or electrogenerated chemiluminescence (ECL) is a kind of luminescence produced during electrochemical reactions in solutions. In electrogenerated chemiluminescence, electrochemically generated intermediates undergo a highly exergonic reaction to produce an electronically excited state that then emits light upon relaxation to a lower-level state. This wavelength of the emitted photon of light corresponds to the energy gap between these two states. ECL excitation can be caused by energetic electron transfer (redox) reactions of electrogenerated species. Such luminescence excitation is a form of chemiluminescence where one/all reactants are produced electrochemically on the electrodes.

<span class="mw-page-title-main">Organoruthenium chemistry</span>

Organoruthenium chemistry is the chemistry of organometallic compounds containing a carbon to ruthenium chemical bond. Several organoruthenium catalysts are of commercial interest and organoruthenium compounds have been considered for cancer therapy. The chemistry has some stoichiometric similarities with organoiron chemistry, as iron is directly above ruthenium in group 8 of the periodic table. The most important reagents for the introduction of ruthenium are ruthenium(III) chloride and triruthenium dodecacarbonyl.

<span class="mw-page-title-main">Stefan Bernhard</span>

Stefan Bernhard is recognized in the scientific community for his work in several applied fields pertaining to the interaction between light and transition metal complexes. His involvement in the prediction, generation, and spectroscopy of circularly polarized luminescence from synthesized chiral phosphors have significantly advanced the state-of-the-art in this relatively young sub-field of photophysical chemistry. Other contributions involve work in artificial photosynthesis and organic light emitting devices.

Photochemical reduction of carbon dioxide harnesses solar energy to convert CO2 into higher-energy products. Environmental interest in producing artificial systems is motivated by recognition that CO2 is a greenhouse gas. The process has not been commercialized.

<span class="mw-page-title-main">Tris(acetonitrile)cyclopentadienylruthenium hexafluorophosphate</span> Chemical compound

Tris(acetonitrile)cyclopentadienylruthenium hexafluorophosphate is an organoruthenium compound with the formula [(C5H5)Ru(NCCH3)3]PF6, abbreviated [CpRu(NCMe)3]PF6. It is a yellow-brown solid that is soluble in polar organic solvents. The compound is a salt consisting of the hexafluorophosphate anion and the cation [CpRu(NCMe)3]+. In coordination chemistry, it is used as a source of RuCp+ for further derivitization. In organic synthesis, it is a homogeneous catalyst. It enables C-C bond formation and promotes cycloadditions. The cyclopentadienyl ligand (Cp) is bonded in an η5 manner to the Ru(II) center.

<span class="mw-page-title-main">Photoredox catalysis</span>

Photoredox catalysis is a branch of photochemistry that uses single-electron transfer. Photoredox catalysts are generally drawn from three classes of materials: transition-metal complexes, organic dyes, and semiconductors. While organic photoredox catalysts were dominant throughout the 1990s and early 2000s, soluble transition-metal complexes are more commonly used today.

Tehshik Peter Yoon is a Canadian-born chemist who studies the new reaction methods for organic synthesis with the use of catalysis. Yoon currently is a professor at the University of Wisconsin–Madison in the chemistry department. For his contributions to science, he has received numerous awards including the Beckman Young Investigator Award and National Science Foundation CAREER Award.

Photo-Induced Cross-Linking of Unmodified Proteins (PICUP) is a protein cross-linking method by visible light irradiation of a photocatalyst in the presence of an electron acceptor and the protein of interest. Irradiation results in a highly reactive protein radical that forms a covalent bond between the amino acid side chains of the proteins to be linked. Cross-linking methods developed prior to PICUP, including the use of physical, oxidative, and chemical cross-linkers, often require more time and result in protein byproducts. In addition, the cross-linked protein yield is very low due to the multifunctionality of the cross-linking reagents.

<i>cis</i>-Dichlorobis(bipyridine)ruthenium(II) Chemical compound

cis-Dichlorobis(bipyridine)ruthenium(II) is the coordination complex with the formula RuCl2(bipy)2, where bipy is 2,2'-bipyridine. It is a dark green diamagnetic solid that is a precursor to many other complexes of ruthenium, mainly by substitution of the two chloride ligands. The compound has been crystallized as diverse hydrates.

The Stahl oxidation is a copper-catalyzed aerobic oxidation of primary and secondary alcohols to aldehydes and ketones. Known for its high selectivity and mild reaction conditions, the Stahl oxidation offers several advantages over classical alcohol oxidations.

Transition metal complexes of 2,2'-bipyridine are coordination complexes containing one or more 2,2'-bipyridine ligands. Complexes have been described for all of the transition metals. Although few have any practical value, these complexes have been influential. 2,2'-Bipyridine is classified as a diimine ligand. Unlike the structures of pyridine complexes, the two rings in bipy are coplanar, which facilitates electron delocalization. As a consequence of this delocalization, bipy complexes often exhibit distinctive optical and redox properties.

<span class="mw-page-title-main">Dichlororuthenium tricarbonyl dimer</span> Chemical compound

Dichlororuthenium tricarbonyl dimer is an organoruthenium compound with the formula [RuCl2(CO)3]2. A yellow solid, the molecule features a pair of octahedral Ru centers bridged by a pair of chloride ligands. The complex is a common starting material in ruthenium chemistry.

<span class="mw-page-title-main">Tris(bipyridine)iron(II) chloride</span> Chemical compound

Tris(bipyridine)iron(II) chloride is the chloride salt of the coordination complex tris(bipyridine)iron(II), [Fe(C10H8N2)3]2+. It is a red solid. In contrast to tris(bipyridine)ruthenium(II), this iron complex is not a useful photosensitizer because its excited states relax too rapidly, a consequence of the primogenic effect.

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