Ruthenium carbonylates, ruthenium carbonyl hydrides, osmium carbonylates and their preparation
AssigneeThe Ohio State University Research Foundation
InventorsSheldon G. Shore, Colleen C. Nagel
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Abstract
Disclosed are the novel cluster compounds [HRu.sub.4 (CO).sub.13 ].sup.1-, [Ru.sub.4 (CO).sub.13 ].sup.2-, [Ru.sub.4 (CO).sub.12 ].sup.4-, [HRu.sub.4 (CO).sub.12 ].sup.3-, and salts thereof, and H.sub.4 Ru.sub.4 (CO).sub.12. Also disclosed are novel procedures for synthesizing these cluster compounds in high yield. Further disclosed is a novel procedure for making H.sub.2 Ru.sub.4 (CO).sub.13 and H.sub.4 Ru.sub.4 (CO).sub.12 in high yield. Also disclosed are [Ru.sub.3 (CO).sub.11 ].sup.2- and the corresponding osmium dianion.
Claims118
A ruthenium carbonylate anion of the formula [H.sub.x Ru.sub.4 (CO).sub.13 ].sup.(2-x)- where x is 0 or 1.
A salt of a ruthenium carbonylate anion of the formula [H.sub.x Ru.sub.4 (CO).sub.13 ].sup.(2-x)- where x is 0 or 1, wherein the cation is an alkali metal, a cation derived from an amine, a quaternary ammonium cation or a phosphonium cation.
A method for making a ruthenium carbonylate complex of the formula [H.sub.y Ru.sub.4 (CO).sub.13 ].sup.(2-y)- where y is 0 or 1 by the controlled reduction of Ru.sub.3 (CO).sub.12 which comprises:
- establishing a reaction mixture held under substantially anhydrous conditions and oxygen-depleted conditions at a temperature not above about room temperature of said Ru.sub.3 (CO).sub.12 ;
- an alkali metal;
- a carrier compound which will carry an electron produced by the ionization of said alkali metal of said Ru.sub.3 (CO).sub.12 ;
- and a solvent which will at least solubilize the electron-bearing form of said carrier compounds, the molar ratio of said alkali metal to said Ru.sub.3 (CO).sub.12 being restricted to be at least about 1.5:1 but less than 3:1.
A method of making [HRu.sub.4 (CO).sub.13 ].sup.1- or H.sub.2 Ru.sub.4 (CO).sub.13 which comprises establishing a reaction mixture comprising a solvent containing the dianion [Ru.sub.4 (CO).sub.13 ].sup.2- dissolved therein and a protic acid under conditions substantially free of molecular oxygen at a temperature not substantially above about room temperature.
A method according to 34 wherein said cation of said salt is an alkali metal.
A method of making [HRu.sub.4 (CO).sub.13 ].sup.1- which comprises reacting H.sub.2 Ru.sub.4 (CO).sub.13 with [Ru.sub.4 (CO).sub.13 ].sup.2- in a solvent.
A method of making H.sub.2 Ru.sub.4 (CO).sub.13 which comprises establishing a reaction mixture comprising a solvent containing the anion [HRu.sub.4 (CO).sub.13 ].sup.1- dissolved therein and a protic acid under conditions substantially free of molecular oxygen at a temperature not substantially above about room temperature.
A ruthenium carbonylate anion of the formula [H.sub.q Ru.sub.4 (CO).sub.12 ].sup.(4-q)- where q is 0 or 1.
A salt of a ruthenium carbonylate anion of the formula [H.sub.q Ru.sub.4 (CO).sub.12 ].sup.(4-q)- where q is 0 or 1, wherein the cation is an alkali metal, a cation derived from an amine, a quaternary ammonium cation or a phosphonium cation.
A method of making a ruthenium carbonyl complex of the general formula [H.sub.r Ru.sub.4 (CO).sub.12 ].sup.(4-r)- where r is 0, 1, 2, 3, or 4 which comprises establishing a reaction mixture held under substantially anhydrous and oxygen depleted conditions at a temperature not above about 80.degree. C., said reaction mixture comprising a ruthenium carbonyl starting material selected from the group consisting of Ru.sub.3 (CO).sub.12 and [Ru.sub.4 (CO).sub.13 ].sup.2-, an alkali metal, a carrier compound which will carry an electron produced by the ionization of said alkali metal to said starting material, and a solvent which will solubilize at least the electron-carrying form of said carrier compound.
A method of making a ruthenium carbonyl complex of the general formula [H.sub.s Ru.sub.4 (CO).sub.12 ].sup.(4-s)- where s is 1, 2, 3, or 4 which comprises establishing a reaction mixture comprising a slurry or a solvent containing the tetraanion [Ru.sub.4 (CO).sub.12 ].sup.4- dissolved therein and a protic acid at a temperature not substantially above about room temperature.
A method of making a ruthenium carbonyl complex of the general formula [H.sub.t Ru.sub.4 (CO).sub.12 ].sup.(4-t)- where t is 2, 3 or 4 which comprises establishing a reaction mixture comprising a solvent containing the trianion [HRu.sub.4 (CO).sub.12 ].sup.3- dissolved therein and a protic acid at a temperature not substantially above about room temperature.
A Group VIII carbonylate anion of the general formula [M.sub.3 (CO).sub.11 ].sup.2- where M is Ru or Os.
A salt of a Group VIII carbonylate anion of the general formula [M.sub.3 (CO).sub.11 ].sup.2- where M is Ru or Os, wherein the cation is an alkali metal, an alkaline earth metal, a cation derived from an amine, a quaternary ammonium cation, a phosphonium cation or an arsonium cation.
A method of making [Ru.sub.3 (CO).sub.11 ].sup.2- by the controlled reduction of Ru.sub.3 (CO).sub.12 which comprises:
- establishing a reaction mixture of said Ru.sub.3 (CO).sub.12 ;
- an alkaline earth metal;
- a carrier compound which will carry an electron produced by the ionization of said alkaline earth metal to said Ru.sub.3 (CO).sub.12 ;
- and a solvent which will at least solubilize the electron-bearing form of said carrier compound, thereby producing Ca[Ru.sub.3 (CO).sub.11 ].
A method of making [Os.sub.3 (CO).sub.11 ].sup.2- by the controlled reduction of Os.sub.3 (CO).sub.12 which comprises:
- establishing a reaction mixture of said Os.sub.3 (CO).sub.12 ;
- an alkali or alkaline earth metal;
- a carrier compound which will carry an electron produced by the ionization of said metal to said Os.sub.3 (CO).sub.12 ;
- and a solvent which will at least solubilize the electron-bearing form of said carrier compound, thereby producing an alkali or alkaline earth metal salt of said [Os.sub.3 (CO).sub.11 ].sup.2-.
Dependencies are inferred from the claim text.