Processes for producing transition metal amides
View Patent ↗Processes are provided for producing transition metal amides. In methods according to this invention, at least a halogenated transition metal and an amine are combined in a solvent to produce an intermediate composition and an alkylated metal or a Grignard reagent is added to the intermediate composition to produce the transition metal amide.
1. A method of producing a metal amide comprising combining at least a halogenated transition metal and an amine composition in a solvent to produce an intermediate composition and combining at least (i) a portion of the intermediate composition and (ii) an alkylated metal or a Grignard reagent to produce at least the transition metal amide, wherein the amine composition comprises a primary amine, a secondary amine, or a diamine.
2. The method of claim 1 wherein the metal amide comprises M 1 (NR 1 R 2 ) n , the halogenated transition metal comprises M 1 X 1 n , the amine composition comprises n(R 1 R 2 NH), the alkylated metal comprises R 3 M 2 , the Grignard reagent comprises R 4 MgX 2 , M 1 is a transition metal atom, M 2 is a non-transition metal atom, each X 1 is independently a halogen atom, a cyclopentadienyl, an indenyl, a fluorenyl, an alcohol, or a substituted phenol, provided that at least one X 1 is a halogen atom, each X 2 is independently a halogen atom, each of R 1 , R 2 , and R 3 is independently an alkyl having from 1 to about 20 carbon atoms, R 4 is independently an alkyl or aryl having from 1 to about 20 carbon atoms, N is nitrogen, H is hydrogen, Mg is magnesium, and n is the valence of M 1 .
3. A method of producing a metal amide comprising combining at least a halogenated transition metal and an amine in a solvent in a container to produce an intermediate composition in the container and adding an alkylated metal or a Grignard reagent to the intermediate composition in the container to produce at least the transition metal amide, wherein the amine composition comprises a primary amine, a secondary amine, or a diamine.
4. The method of claim 3 wherein the metal amide comprises M 1 (NR 1 R 2 ) n , the halogenated transition metal comprises M 1 X 1 n , the amine composition comprises n(R 1 R 2 NH), the alkylated metal comprises R 3 M 2 , the Grignard reagent comprises R 4 MgX 2 , M 1 is a transition metal atom, M 2 is a non-transition metal atom, each X 1 is independently a halogen atom, a cyclopentadienyl, an indenyl, a fluorenyl, an alcohol, or a substituted phenol, provided that at least one X 1 is a halogen atom, each X 2 is independently a halogen atom, each of R 1 , R 2 , and R 3 is independently an alkyl having from 1 to about 20 carbon atoms, R 4 is independently an alkyl or aryl having from 1 to about 20 carbon atoms, N is nitrogen, H is hydrogen, Mg is magnesium, and n is the valence of M 1 .
5. A method of producing a metal amide, comprising (a) combining at least a halogenated transition metal and an amine composition in a solvent to produce a first intermediate composition, (b) combining at least (i) a portion of the first intermediate composition and (ii) a portion of an alkylated metal or a Grignard reagent to produce a second intermediate composition, and (c) combining at least (i) a portion of the second intermediate composition and (ii) a portion of the alkylated metal or the Grignard reagent to produce the transition metal amide, wherein the amine composition comprises a primary amine, a secondary amine, or a diamine.
6. The method of claim 5 wherein the metal amide comprises M 1 (NR 1 R 2 ) n , the halogenated transition metal comprises M 1 X 1 n , the amine composition comprises n(R 1 R 2 NH), the alkylated metal comprises R 3 M 2 , the Grignard reagent comprises R 4 MgX 2 , M 1 is a transition metal atom, M 2 is a non-transition metal atom, each X 1 is independently a halogen atom, a cyclopentadienyl, an indenyl, a fluorenyl, an alcohol, or a substituted phenol, provided that at least one X 1 is a halogen atom, each X 2 is independently a halogen atom, each of R 1 , R 2 , and R 3 is independently an alkyl having from 1 to about 20 carbon atoms, R 4 is independently an alkyl or aryl having from 1 to about 20 carbon atoms, N is nitrogen, H is hydrogen, Mg is magnesium, and n is the valence of M 1 .
7. A method of producing a metal amide M 1 (NR 1 R 2 ) n comprising combining at least a halogenated transition metal M 1 X 1 n and an amine n(R 1 R 2 NH) in a solvent to produce an intermediate composition comprising M 1 X 1 (n-x) (NR 1 R 2 ) x .y(R 1 R 2 NH) and combining at least (i) a portion of the intermediate composition and (ii) an alkylated metal R 3 M 2 or a Grignard reagent R 4 MgX 2 in amounts such that the alkylated metal or Grignard reagent is in a stoichiometric amount as to the M 1 X 1 (n-x) (NR 1 R 2 ) x .y(R 1 R 2 NH), such as to produce at least the transition metal amide, wherein M 1 is a transition metal atom, M 2 is a non-transition metal atom, each X 1 is independently a halogen atom, a cyclopentadienyl, an indenyl, a fluorenyl, an alcohol, or a substituted phenol, provided that at least one X 1 is a halogen atom, each X 2 is independently a halogen atom, each of R 1 , R 2 , and R 3 is independently an alkyl having from 1 to about 20 carbon atoms, R 4 is independently an alkyl or aryl having from 1 to about 20 carbon atoms, N is nitrogen, H is hydrogen, Mg is magnesium, and n is the valence of M 1 .
8. A method of producing a metal amide M 1 (NR 1 R 2 ) n comprising (a) combining at least a halogenated transition metal M 1 X 1 n and an amine n(R 1 R 2 NH) in a solvent to produce a first intermediate composition comprising M 1 X 1 (n-x) (NR 1 R 2 ) x .y(R 1 R 2 NH), (b) combining at least (i) a portion of the first intermediate composition and (ii) a portion of an alkylated metal R 3 M 2 or a Grignard reagent R 4 MgX 2 to produce a second intermediate composition, and (c) combining at least (i) a portion of the second intermediate composition and (ii) a portion of the alkylated metal R 3 M 2 or Grignard reagent R 4 MgX 2 in amounts such that the alkylated metal or Grignard reagent is in a stoichiometric amount as to the M 1 X 1 (n-x) (NR 1 R 2 ) x .y(R 1 R 2 NH), such as to produce at least the transition metal amide, wherein M 1 is a transition metal atom, M 2 is a non-transition metal atom, each X 1 is independently a halogen atom, a cyclopentadienyl, an indenyl, a fluorenyl, an alcohol, or a substituted phenol, provided that at least one X 1 is a halogen atom, each X 2 is independently a halogen atom, each of R 1 , R 2 , and R 3 is independently an alkyl having from 1 to about 20 carbon atoms, R 4 is independently an alkyl or aryl having from 1 to about 20 carbon atoms, N is nitrogen, H is hydrogen, Mg is magnesium, and n is the valence of M 1 .