Tris(bipyridine)ruthenium(II) chloride

Structure of [Ru(bipy)3]2+

Other names
Ru-bipy
Ruthenium-tris(2,2’-bipyridyl) dichloride
Identifiers
14323-06-9, (anhydrous)
CAS number
50525-27-4 (hexahydrate)
RTECS number VM2730000
Properties
640.53 g/mol (anhydrous)
Molar mass
748.62 g/mol (hexahydrate)
Appearance red-orange solid
Density solid
Melting point >300 °C
Solubility in water Soluble
Structure
Molecular shape Octahedral
Dipole moment 0D
Hazards
R-phrases none
S-phrases S22 S24/25
Related compounds
Related compounds Ruthenium trichloride
Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
Infobox references

Tris(bipyridine)ruthenium(II) dichloride is the coordination compound with the

formula [Ru(bipy)3]Cl2. This orange crystalline salt is obtained as the hexahydrate,
although all of the properties of interest are in the cation [Ru(bipy)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

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(bipy)3]2+ is an octahedral coordination
complex. The complex is chiral, with D3 symmetry. It has been resolved into its
enantiomers, which are kinetically stable.

Photochemistry of [Ru(bipy)3]2+

[Ru(bipy)3]2+ absorbs UV light and visible light. An aqueous solution absorbs at 452 (+/-
3 nm) with an extinction coefficient of 11,500 M−1cm−1. Solutions of the resulting excited
state have a comparatively long lifetime of 600 nanoseconds in acetonitrile and 400 ns in
water. The excited state relaxes to the ground state by emission of a photon at the
wavelength of 600 nm. 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 often
slow.

The triplet excited state has both oxidizing and reducing properties. This unusual
situation arises because the excited state can be described as an Ru3+ complex containing
a bipy- ligand. Thus, the photochemical properties of [Ru(bipy)3]2+ are reminiscent of the
photosynthetic assembly, which also involves separation of an electron and a hole.[2]

[Ru(bipy)3]2+ has been examined as a photosensitiser for both the oxidation and reduction
of water. Upon absorbing a photon, [Ru(bipy)3]2+ converts to the aforementioned triplet
state, denoted [Ru(bipy)3]2+*. This species transfers an electron, located on one bipy
ligand, to a sacrificial oxidant such as persulfate (S2O82-). The resulting [Ru(bipy)3]3+ is a
powerful oxidant and oxidizes water into O2 and protons via a metal oxide catalyst.[3]
Alternatively, the reducing power of [Ru(bipy)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(bipy)3]2+ are numerous.[4][5] Such complexes are widely discussed for
applications in biodiagnostics, photovoltaics and organic light-emitting diode, but no
derivative has been commercialized.