Metal complexes and methods of making the same
Disclosed herein are embodiments of metal complexes and methods of making the same. The disclosed method embodiments provide a one-step approach to making metal complexes, such as complexes comprising lanthanide metals, rare earth metals, transition metals, main group metals, and/or actinide metals that can be used various applications, such as in separations technology, catalysis (e.g., catalysts for pharmaceutical synthesis and/or catalysts for biomass conversion), nuclear chemistry, LED phosphors, scintillator materials, magnetic materials, and nuclear fuels.
1. A method, comprising heating a reaction mixture to provide a metal complex, wherein:
(i) the reaction mixture comprises
a metal precursor selected from La 0 , Ce 0 , Nd 0 , Dy 0 , Sm 0 , Th 0 , Y 0 , Er 0 , Eu 0 , Gd 0 , Ho 0 , L 0 , Mn 0 , Pr 0 , Sc 0 , Tb 0 , Tm 0 , V 0 , Zn 0 , or Yb 0 ;
pyridine; and
a silicon-containing reagent having a structure according to a formula (R)(R′)(R″)SiX, wherein each of R, R′, and R″ independently are selected from straight-chain C 1-10 alkyl and X is —Cl, —Br, or —I; and
(ii) the metal complex has a structure according to a formula MX n (pyridine) m , wherein
M is selected from La, Ce, Nd, Dy, Sm, Th, Y, Er, Eu, Gd, Ho, Lu, Mn, Pr, Sc, Tb, Tm, V, Zn, or Yb;
X is —Cl, —Br, or —I;
n is an integer ranging from 2 to 6; and
m is an integer ranging from 1 to 5.
2. The method of claim 1 , wherein heating comprises heating the reaction mixture at a temperature ranging from 40° C. to 150° C.
3. The method of claim 1 , wherein heating comprises heating the reaction mixture at a temperature ranging from 80° C. to 100° C.
4. The method of claim 1 , further comprising isolating the metal complex by filtering and washing the metal complex with a solvent in which the metal complex is not soluble.
5. The method of claim 4 , wherein the solvent is pentane or hexanes.
6. The method of claim 1 , further comprising eliminating pyridine from the metal complex to provide a compound having a formula MX n , wherein M is selected from La, Ce, Nd, Dy, Sm, Th, Y, Er, Eu, Gd, Ho, Lu, Mn, Pr, Sc, Tb, Tm, V, Zn, or Yb; X is —Cl, —Br, or —I; and n is an integer ranging from 2 to 6.
7. The method of claim 6 , wherein eliminating comprises heating the metal complex and/or applying vacuum pressure.
8. The method of claim 7 , wherein heating comprises using a temperature ranging from 25° C. to 700° C.
9. The method of claim 1 , wherein 1.5 equivalents to 20 equivalents of the silicon-containing reagent, relative to the metal precursor, are used.
10. The method of claim 1 , wherein each of R, R′, and R″ independently are selected from methyl or ethyl.
11. The method of claim 1 , wherein the metal complex is selected from LaCl 3 (pyridine) 4 , CeCl 3 (pyridine) 4 , NdCl 3 (pyridine) 4 , DyCl 3 (pyridine) 4 , SmCl 3 (pyridine) 4 , ThCl 4 (pyridine) 4 , YCl 3 (pyridine) 4 , ErCl 3 (pyridine) 4 , GdCl 3 (pyridine) 4 , HoCl 3 (pyridine) 4 , LuCl 3 (pyridine) 4 , MnCl 2 (pyridine) 2 , PrCl 3 (pyridine) 4 , ScCl 3 (pyridine), TbCl 3 (pyridine) 4 , TmCl 3 (pyridine) 4 , VCl 2 (pyridine) 4 , ZnCl 2 (pyridine) 2 , YbCl 3 (pyridine) 4 , LaBr 3 (pyridine) 4 , NdBr 3 (pyridine) 4 , DyBr 3 (pyridine) 4 , SmBr 3 (pyridine) 4 , SmBr 2 (pyridine) 5 , ErBr 3 (pyridine) 4 , EuBr 2 (pyridine) 5 , GdBr 3 (pyridine) 4 , HoBr 3 (pyridine) 4 , LuBr 3 (pyridine) 4 , PrBr 3 (pyridine) 4 , TbBr 3 (pyridine) 4 , ThBr 4 (pyridine) 4 , TmBr 3 (pyridine) 4 , ZnBr 2 (pyridine) 2 , YbBr 3 (pyridine) 4 , YbBr 2 (pyridine) 4 , SmI 2 (pyridine) 5 , EuI 2 (pyridine) 4 , or YbI 2 (pyridine) 4 .
12. A method, comprising heating a reaction mixture to provide a metal complex, wherein:
(i) the reaction mixture comprises
a metal precursor selected from La 0 , Ce 0 , Nd 0 , Dy 0 , Sm 0 , Th 0 , Y 0 , Er 0 , Eu 0 , Gd 0 , Ho 0 , Lu 0 , Mn 0 , Pr 0 , Sc 0 , Tb 0 , Tm 0 , V 0 , Zn 0 , or Yb 0 ;
pyridine; and
a silicon-containing reagent selected from Me 3 SiCl, Me 3 SiBr, or Me 3 SiI; and
(ii) the metal complex has a structure according to a formula MX n (pyridine) m , wherein
M is selected from La, Ce, Nd, Dy, Sm, Th, Y, Er, Eu, Gd, Ho, Lu, Mn, Pr, Sc, Tb, Tm, V, Zn, or Yb;
X is —Cl, —Br, or —I;
n is an integer ranging from 2 to 6; and
m is an integer ranging from 1 to 5.
13. The method of claim 12 , wherein heating comprises heating the reaction mixture at a temperature ranging from 40° C. to 150° C.
14. The method of claim 12 , wherein heating comprises heating the reaction mixture at a temperature ranging from 80° C. to 100° C.
15. The method of claim 12 , further comprising isolating the metal complex by filtering and washing the metal complex with a solvent in which the metal complex is not soluble.
16. The method of claim 12 , further comprising eliminating pyridine from the metal complex to provide a compound having a formula MX n , wherein M is selected from La, Ce, Nd, Dy, Sm, Th, Y, Er, Eu, Gd, Ho, Lu, Mn, Pr, Sc, Tb, Tm, V, Zn, or Yb; X is —Cl, —Br, or —I; and n is an integer ranging from 2 to 6.
17. The method of claim 16 , wherein eliminating comprises heating the metal complex using a temperature ranging from 25° C. to 700° C.; and/or applying vacuum pressure.