Metal cyanide complexes

Abstract

Metal cyanide complexes of a single metal or mixed-metal complexes in which a metal is complexed with cyanide. The metals preferably include .[.magnesium, beryllium, aluminum,.]. chromium, titanium, zirconium, thorium, yttrium and cobalt and nickel in addition to the lanthanide metals. An aqueous solution is prepared and the complex is isolated by crystallization with a stoichiometry of the metals determined by their proportions in the solution.

We claim: 
     
       1. A metal-metal cyanide complex selected from the group which consists of: .[.Mg [Mg (CN) 4  ], Be [Be (CN) 4  ], Al [Al (CN) 6  ],.]. Ti [Ti (CN).sub. 8 ], Zr [Zr (CN) 8  ], Th [Th (CN) 8  ], .Iadd.and .Iaddend.Y [Y (CN) 6  ]. .[.and Ln [Ln (CN) 6  ], wherein Ln represents a lanthanide element with an atomic number between 57 and 71 inclusive..]. 
     
     
       2. A metal-metal cyanide complex selected from the group which consists of: cobaltocyanic lanthanide of the formula   Ln.sub.x H.sub.4y-3r [Co(CN).sub.6 ].sub.Y       where y ≧ 1 and 0<x-4/3 Y;  cobalticyanic lanthanide   Ln.sub.x H.sub.3y-3x [Co(CN).sub.6 ].sub.Y       where y ≧ 1 and 0<x< y;  chromicyanic lanthanide   Ln.sub.x H.sub.3y-3x [Cr(CN).sub.6 ].sub.Y       where y ≧ 1 and 0<x< y;  nickelocyanic lanthanide   Ln.sub.x H.sub.2y-3x [Ni(CN).sub.4 ].sub.Y       where y ≧1 and 0<x≦  2/3 Y;  cobaltocyanic polylanthanide   Ln'.sub.x Ln".sub.z . . . H.sub.4y-3x-3z . . . [Co(CN).sub.6 ].sub.7       where y ≧ 1, 0< x<4/3 y   where 0<z< 4/3 y,   and 4y-3x-3z ≧ 0; cobalticyanic polylanthanide   Ln'.sub.x Ln".sub.z . . . H.sub.3y-3x-3z [Co(CN).sub.6 ].sub.y       where y ≧ 1, 0 <x< y and 0 <z<y3y-3x-3z ≦ 0;  chromicyanic polylanthanide   Ln'.sub.x Ln".sub.z . . . H.sub.3y-3x-3z . . . [Cr(CN).sub.6 ].sub.Y       where y ≧ 1, 0 <x<y, 0 <z<y, and 3y-3x-3z ≧ 0;  nickelocyanic polylanthanide   Ln'.sub.x Ln".sub.z . . . H.sub.2y- 3x- 3z . . . [Ni(CN).sub.4 ].sub.Y       where y >1, 0 <x<  2/3 Y,   < z<  2/3  y, and   2y-3x-3z ≧ 0;   .[.polylanthanide cyanide complexes of the general formula.].   .[.Dn.sub.x ' Ln.sub.z " . . . H.sub.3y-3x-3z . . . [Ln (CN).sub.6 ].sub. Y .].     .[. in which Ln, Ln', Ln" . . . represent elements of the lanthanide series having an atomic number between 57 and 71 inclusive or yttrium and the coefficients x, y and z have the relationships.].     .[. y ≧ 1, 0 ≦ x ≦ y, 0 ≦ z ≦ y and 3y-3x-3z  ≧ 0;.].     .[. the lanthanide cyanides of aluminum of the general formula.].     .[. Al.sub.x H.sub.3y-3x [Ln (CN).sub.6 ].sub.Y .].     .[. in which Ln represents a lanthanide element having an atomic number between 57 and 71 inclusive or yttrium and the coefficients x and y are selected such that.].     .[. y ≧ 1 and 0 ≦x≦y;.].     the cobalticyanides of lanthanides and of bivalent metals of the general formula     Ln.sub.x M.sub.z H.sub.3y-3x-2z [Co.sup.III (CN).sub.6 ].sub.y     in which M represents a bivalent metal, where Ln represents a lanthanide series element having an atomic number between 57 and 71 inclusive and x, y and z are selected such that     Y > 1, 0 <x < y, 0 < z < y and 3y-3x-3z ≧ 0;     the cobalticyanides of a plurality of lanthanide elements and a bivalent metal wherein M may be selected from the alkaline earth metals and having the general formula     Ln'.sub.x"  Ln".sub.x"  . . . M.sub.z H.sub.3y-2z-3x' -3x " . . . [Co.sup.III (CN).sub.6 ].sub.y     where Ln', Ln" . . . are lanthanide elements with atomic number between 57 and 71 and y >km 0 <x' < y, 0 < x" < y, 0 < z < y and 3y-2z-3x'-3x" . . . ≧  0.   .[.the polymetallic complexes of the general formula.].     .[. H.sub.3-n M.sub.m/v M'.sub.p' /r . . . [Al (CN).sub.6 ].].     .[. where 0 < n < 3 and m + p + . . . = n, M, M' . . . being metallic cations with valences v, v' . . . or the ammonium ion m, p' . . . being coefficients balancing the electrical charge of the molecule..].     
     
     
       3. A process for preparing a metal cyanide comprising the steps of forming a metal cyanide complex in aqueous solution and crystallizing the complex salt from said solution, said cyanide complex being formed in solution by reacting a complex acid of the general formula H y , where M is a metal forming part of the complex, X is the coordination number of the metal and y and p are selected to insure charge balance in the molecule, with a hydroxide, oxide or carbonate of a metal which may be the same as the metal of said acid or different, said metals being selected from the group which consists of .[.magnesium, beryllium, aluminum,.]. chromium, titanium, zirconium, thorium, yttrium, cobalt, nickel and the elements of the lanthanide series having an atomic number between 57 and 71 inclusive. 
     
     
       4. The process defined in claim 3 wherein the complex which is crystallized from said aqueous solution is a monometallic complex and the metal of said acid is identical to the metal of said hydroxide, oxide or carbonate. 
     
     
       5. A process for preparing a metal cyanide comprising the steps of forming a metal cyanide complex in aqueous solution and crystallizing the complex salt from said solution, said complex being formed in solution by reacting hydrocyanic acid in an aqueous solution with the hydroxides, oxides, carbonates or acetates of at least two different metals selected from the group which consists of .[.magnesium, beryllium, aluminum,.]. chromium, titanium, zirconium, thorium, yttrium, cobalt, nickel and the elements of the lanthanide series having an atomic number between 57 and 71 inclusive. 
     
     
       6. The process defined in claim 5 wherein the hydrocyanic acid is used at a concentration of 10 to 60 percent by weight and is provided in an excess of 10 to 20 percent over that which can react with the compounds of said metals. 
     
     
       7. The process defined in claim 3 wherein said crystals are formed from said aqueous solution by evaporating said aqueous solution under vacuum at a temperature of 40° to 60° C. 
     
     
       8. The process defined in claim 3 wherein said crystals are formed from said aqueous solution by azeotropically removing water therefrom. .Iadd.9. A metal-metalcyanide complex selected from the group which consists of: chromium (III) hexacyanochromate;   titanium (IV) octacyanotitanate;   zirconium (IV) octacyanozirconate; and   thorium (IV) octacyanothorate. .Iaddend..Iadd.10. The metal-metalcyanide complex defined in claim 9 which is:   chromium (III) hexacyanochromate. .Iaddend..Iadd.11. The metal-metalcyanide complex defined in claim 9 which is:   titanium (IV) octacyanotitanate. .Iaddend..Iadd.12. The metal-metalcyanide complex defined in claim 9 which is:   zirconium (IV) octacyanozirconate. .Iaddend..Iadd.13. The metal-metalcyanide complex defined in claim 9 which is:   thorium (IV) octacyanothorate. .Iaddend.