Method for synthesizing metal bis(borano) hypophosphite complexes
View Patent ↗The present invention describes the synthesis of a family of metal bis(borano) hypophosphite complexes. One procedure described in detail is the syntheses of complexes beginning from phosphorus trichloride and sodium borohydride. Temperature, solvent, concentration, and atmosphere are all critical to ensure product formation. In the case of sodium bis(borano) hypophosphite, hydrogen gas was evolved upon heating at temperatures above 150° C. Included in this family of materials are the salts of the alkali metals Li, Na and K, and those of the alkaline earth metals Mg and Ca. Hydrogen storage materials are possible. In particular the lithium salt, Li[PH 2 (BH 3 ) 2 ], theoretically would contain nearly 12 wt % hydrogen. Analytical data for product characterization and thermal properties are given.
1. A method for synthesizing a metal bis(borano) hypophosphite complex (M[PH 2 (BH 3 ) 2 ] x ), comprising the steps of:
preparing a first suspension solution of an alkali or alkaline earth metal borohydride compound with a first quantity of a first dry solvent within a first closed container;
preparing a second suspension solution of phosphorous trichloride with a second quantity of the first dry solvent within a second closed container;
cooling the first and second closed containers and their contents to a temperature below 0° C.;
adding the second suspension solution to the first suspension solution contained within the first closed container to provide a reaction solution;
mixing the cold reaction solution at ambient temperature conditions and allowing the reaction solution to warm to room temperature;
removing all or most of the first dry solvent from the first closed container to provide a solid residue;
adding a quantity of a second solvent to the solid residue to form a third suspension solution;
filtering the third suspension solution through a quantity of diatomaceous earth to provide a first filtrate liquid and a quantity of solid material deposited on the quantity of diatomaceous earth;
collecting the first filtrate liquid; and
removing the second solvent and any remaining first solvent from the first filtrate liquid under vacuum to provide white solid material comprising M[PH 2 (BH 3 ) 2 ] x , where M is an alkali or alkaline earth metal and where x=1 or 2 based upon the valence of M.
2. The method of claim 1 , wherein the alkali or alkaline earth metal is Li, Na, K, Mg, or Ca.
3. The method of claim 1 , wherein the first and second closed containers comprise an inert atmosphere.
4. The method of claim 1 , wherein the phosphorous trichloride is present in an amount less than that which would be required to completely consume the borohydride compound.
5. The method of claim 1 , wherein the step of removing the second solvent and any remaining first solvent further comprising heating the first filtrate liquid to 60° C. under vacuum.
6. The method of claim 1 , wherein the step of filtering the third suspension solution further comprises washing the quantity of solid material deposited on the quantity of diatomaceous earth a second and a third time with a quantity of the second solvent to provide a second and third filtrate liquid.
7. The method of claim 6 , wherein the second and third filtrate liquids are collected after each wash and added to the first filtrate liquid.
8. The method of claim 7 , wherein the step of removing the second solvent and any remaining first solvent further comprises heating the first, second and third filtrate liquids to 60° C. under vacuum.
9. The method of claim 1 , wherein the step of cooling comprises cooling the first and second closed containers and their contents to a temperature of about −78° C.
10. The method of claim 1 , wherein the first solvent is 1,2-dimethoxyethane.
11. The method of claim 1 , wherein the second solvent is diethyl ether.