Ruthenium(III) chloride
Ruthenium(III) chloride is the chemical compound with the formula RuCl. "Ruthenium(III) chloride" more commonly refers to the hydrate RuCl·"x"HO. Both the anhydrous and hydrated species are dark brown or black solids. The hydrate, with a varying proportion of water of crystallization, often approximating to a trihydrate, is a commonly used starting material in ruthenium chemistry. Preparation and properties. Anhydrous ruthenium(III) chloride is usually prepared by heating powdered ruthenium metal with chlorine. In the original synthesis, the chlorination was conducted in the presence of carbon monoxide, the product being carried by the gas stream and crystallising upon cooling. Two  allotropes of RuCl are known. The black α-form adopts the CrCl-type structure with long Ru-Ru contacts of 346 pm. This allotrope has honeycomb layers of Ru which are surrounded with an octahedral cage of Cl anions. The ruthenium cations are magnetic residing in a low-spin J~1/2 ground state with net angular momentum L=1. Layers of α-RuCl are stacked on top of each other with weak Van-der-Waals forces. These can be cleaved to form mono-layers using scotch tape. The dark brown metastable β-form crystallizes in a hexagonal cell; this form consists of  infinite chains of face-sharing octahedra with Ru-Ru contacts of 283 pm, similar to the structure of zirconium trichloride. The β-form is irreversibly converted to the α-form at 450–600 °C. The β-form is diamagnetic, whereas α-RuCl is paramagnetic at room temperature. RuCl vapour decomposes into the elements at high temperatures ; the enthalpy change at 750 °C (1020 K), Δ"H" has been estimated as +240 kJ/mol. Solid state physics. α-RuCl was proposed as a candidate for a Kitaev quantum spin liquid state when neutron scattering revealed an unusual magnetic spectrum, and thermal  transport revealed chiral Majorana Fermions when subject to a magnetic field. Coordination chemistry of hydrated ruthenium trichloride. As the most commonly available ruthenium compound, RuCl·"x"HO is the precursor to many hundreds of chemical compounds. The noteworthy property of ruthenium complexes, chlorides and otherwise, is the existence of more than one oxidation state, several of which are kinetically inert. All second and third-row transition metals form exclusively low spin complexes, whereas ruthenium is special in the stability of adjacent oxidation states, especially Ru(II), Ru(III) (as in the parent RuCl·"x"HO) and Ru(IV). This reaction proceeds via the intermediate cis-Ru(bipy)Cl. [RuCl(CMe )] can be further reduced to [RuCl(CMe)]. Illustrative complexes derived from "ruthenium trichloride". Some of these compounds were utilized in the research related to two Nobel Prizes. Noyori was awarded the Nobel Prize in Chemistry in 2001 for the development of practical asymmetric hydrogenation catalysts based on ruthenium. Robert H. Grubbs was awarded the Nobel Prize in Chemistry in 2005 for the development of practical alkene metathesis catalysts based on ruthenium alkylidene derivatives. Carbon monoxide derivatives. RuCl(HO) reacts with carbon monoxide under mild conditions. In contrast, iron chlorides do not react with CO. CO reduces the red-brown trichloride to yellowish  Ru(II) species. Specifically, exposure of an ethanol solution of RuCl(HO) to 1 atm of CO gives, depending on the specific conditions, [RuCl(CO)], [RuCl(CO)], and [RuCl(CO)]. Addition of ligands (L) to such solutions gives Ru-Cl-CO-L compounds (L = PR). Reduction of these carbonylated solutions with Zn affords the orange triangular cluster Ru(CO).