Volatile metal β-ketoiminate and metal β-diiminate complexes
View Patent ↗Metal ketoiminate or diiminate complexes, containing copper, silver, gold, cobalt, ruthenium, rhodium, platinum, palladium, nickel, osmium, or indium, and methods for making and using same are described herein. In certain embodiments, the metal complexes described herein may be used as precursors to deposit metal and metal-containing films on a substrate through, for example, atomic layer deposition or chemical vapor deposition conditions.
1. A metal complex represented by formula (I):
wherein M is a metal selected from Cu, Au, Ag, Co, Ru, Rh, Pt, In, Pd, Ni, and Os;
wherein X is selected from oxygen and NR 5 ;
wherein R 1 , R 2 , R 3 , and R 5 are each independently selected from a hydrogen atom; a halogen atom; a nitro group having a formula NO 2 ; an alkyl having a formula C n H 2n+1 wherein n is a number ranging from 1 to 20; a fluoroalkyl having the formula C n H x F y wherein the product of the (x+y) equals the product of (2n+1) and n is a number ranging from 1 to 20; an alkylsilane having a formula (R 6 ) 3 Si wherein R 6 is each independently an alkyl, an alkoxy or an amide comprising from 1 to 20 carbon atoms; an aryl group comprising from 6 to 12 carbon atoms; an alkyl-substituted aryl comprising from 6 to 12 carbon atoms; a fluoroalkyl substituted aryl comprising from 6 to 12 carbon atoms; a fluoroaryl comprising from 6 to 12 carbon atoms; an ether having a formula (CH 2 ) n O(C m H 2m+1 ) where n and m are independently a number ranging from 1 to 20; a fluoroether having a formula (C n H x F y )O(C m H w F z ) wherein (x+y)=2n, (w+z)=(2m+1), and n and m are each independently a number ranging from 1 to 20; a silylether having a formula (R 7 ) 3 SiO wherein R 7 is each independently an alkyl comprising from 1 to 20 carbon atoms or an aryl comprising from 6 to 12 carbon atoms; an alkoxy comprising from 1 to 20 carbon atoms; and an amide comprising from 1 to 20 carbon atoms;
wherein R 4 is selected from an alkyl having a formula C n H 2n+1 wherein n is a number ranging from 1 to 20; a fluoroalkyl having the formula C n H x F y wherein the product of the (x+y) equals the product of (2n+1) and n is a number ranging from 1 to 20; an alkylsilane having a formula (R 6 ) 3 Si wherein R 6 is each independently an alkyl, an alkoxy or an amide comprising from 1 to 20 carbon atoms; an aryl comprising from 6 to 12 carbon atoms; an alkyl-substituted aryl comprising from 6 to 12 carbon atoms; a fluoroalkyl substituted aryl comprising from 6 to 12 carbon atoms; a fluoroaryl comprising from 6 to 12 carbon atoms; an ether having a formula (CH 2 ) n O(C m H 2m+1 ) where n and m are independently a number ranging from 1 to 20; a fluoroether having a formula (C n H x F y )O(C m H w F z ) wherein (x+y)=2n, (w+z)=(2m+1), and n and m are each independently a number ranging from 1 to 20; a silylether having a formula (R 7 ) 3 SiO wherein R 7 is each independently an alkyl group comprising from 1 to 20 carbon atoms or an aryl group comprising from 6 to 12 carbon atoms; an alkoxy comprising from 1 to 20 carbon atoms; and an amide comprising from 1 to 20 carbon atoms and wherein R 4 associates with L by having a hydrogen, an atom, or a group removed;
wherein L is a ligand selected from an alkylnitrile comprising from 2 to 20 carbon atoms; a silylnitrile having the formula (R 8 ) 3 SiCN wherein R 8 is each independently an alkyl, an alkoxy, or an amide comprising from 1 to 20 carbon atoms; an alkyne comprising from 1 to 20 carbon atoms; a silylalkyne having a formula (R 9 ) 3 SiCCR 10 wherein R 9 is each independently an alkyl, an amide, or an alkoxy comprising from 1 to 20 carbon atoms and R 10 is hydrogen, an alkoxy, an amide, or an alkyl comprising from 1 to 20 carbon atoms; a silylalkyne having a formula (R 11 ) 3 SiCCSi(R 11 ) 3 wherein R 11 is each independently an alkyl, an amide, or an alkoxy comprising from 1 to 20 carbon atoms; an alkene, diene, or triene comprising from 1 to 20 carbon atoms; a silylalkene having a formula (R 12 ) 3 SiCR 13 C(R 13 ) 2 wherein R 12 is each independently an alkyl, an alkoxy, an aryl, a vinyl, or an amide comprising from 1 to 20 carbon atoms and R 13 is each independently a hydrogen, an alkyl comprising from 1 to 20 carbon atoms, or an aryl comprising from 6 to 12 carbon atoms; a bis(silyl)alkene having the formula (R 14 ) 3 SiCR 13 CR 13 Si(R 14 ) 3 wherein R 14 is each independently an alkyl, an alkoxy, or an amide comprising from 1 to 20 carbon atoms and R 13 is each independently a hydrogen atom or an alkyl comprising from 1 to 20 carbon atoms; an allene comprising from 3 to 20 carbons; an allene having a formula (R 15 ) 2 CCC(R 15 ) 2 where R 15 is each independently a hydrogen atom or an alkyl silane having a formula (R 16 ) 3 Si wherein R 16 is each independently an alkyl, an amide, or an alkoxy comprising from 1 to 20 carbon atoms; an alkylisocyanide having a formula R 17 NC wherein R 17 is an alkyl comprising from 1 to 20 carbon atoms; a silylisocyanide having a formula (R 18 ) 3 SiNC wherein R 18 is each independently an alkyl comprising from 1 to 20 carbon atoms; and an aryl group comprising from 6 to 12 carbon atoms and wherein L associates with R 4 by having a hydrogen, an atom, or a group removed; and wherein an organometallic bond between M and L is selected from two single bonds or one single bond.
2. The complex of claim 1 wherein M is Cu.
3. The complex of claim 1 , wherein X is O.
4. The complex of claim 3 wherein at least one of substituents R 1 , R 2 , and/or R 3 connects with R 4 provided that R 1 , R 2 , and/or R 3 are not the hydrogen atom, the halogen atom, or the nitro group having the formula NO 2 .
5. The complex of claim 1 wherein at least one of substituents R 1 , R 2 , and/or R 3 connects with R 4 to form a cyclic structure.
6. The complex of claim 1 wherein X is NR 5 .
7. The complex of claim 6 wherein R 5 is associated with ligand L and a hydrogen, an atom, or a group removed.
8. The complex of claim 7 wherein the complex has an additional ligand L associated with R 5 .
9. The complex of claim 6 wherein at least one of substituents R 1 , R 2 , R 3 , and/or R 5 connects with R 5 provided that R 1 , R 2 , R 3 and/or R 5 are not the hydrogen atom, the halogen atom, or the nitro group having the formula NO 2 .
10. The complex of claim 1 wherein at least one of substituents R 1 , R 2 , and/or R 3 connects with R 5 to form a cyclic structure.
11. A method for depositing a film comprising metal on a substrate, the method comprising:
contacting the substrate with a metal complex having formula (I) wherein the contacting is conducted at conditions sufficient for the complex to react and form the film
wherein M is a metal selected from Cu, Au, Ag, Co, Ru, Rh, Pt, In, Pd, Ni, and Os;
wherein X is selected from oxygen and NR 5 ;
wherein R 1 , R 2 , R 3 , and R 5 are each independently selected from a hydrogen atom; a halogen atom; a nitro group having a formula NO 2 ; an alkyl having a formula C n H 2n+1 wherein n is a number ranging from 1 to 20; a fluoroalkyl having the formula C n H x F y wherein the product of the (x+y) equals the product of (2n+1) and n is a number ranging from 1 to 20; an alkylsilane having a formula (R 6 ) 3 Si wherein R 6 is each independently an alkyl, an alkoxy or an amide comprising from 1 to 20 carbon atoms; an aryl group comprising from 6 to 12 carbon atoms; an alkyl-substituted aryl comprising from 6 to 12 carbon atoms; a fluoroalkyl substituted aryl comprising from 6 to 12 carbon atoms; a fluoroaryl comprising from 6 to 12 carbon atoms; an ether having a formula (CH 2 ) n O(C m H 2m+1 ) where n and m are independently a number ranging from 1 to 20; a fluoroether having a formula (C n H x F y )O(C m H w F z ) wherein (x+y)=2n, (w+z)=(2m+1), and n and m are each independently a number ranging from 1 to 20; a silylether having a formula (R 7 ) 3 SiO wherein R 7 is each independently an alkyl comprising from 1 to 20 carbon atoms or an aryl comprising from 6 to 12 carbon atoms; an alkoxy comprising from 1 to 20 carbon atoms; and an amide comprising from 1 to 20 carbon atoms;
wherein R 4 is selected from an alkyl having a formula C n H 2n+1 wherein n is a number ranging from 1 to 20; a fluoroalkyl having the formula C n H x F y wherein the product of the (x+y) equals the product of (2n+1) and n is a number ranging from 1 to 20; an alkylsilane having a formula (R 6 ) 3 Si wherein R 6 is each independently an alkyl, an alkoxy or an amide comprising from 1 to 20 carbon atoms; an aryl comprising from 6 to 12 carbon atoms; an alkyl-substituted aryl comprising from 6 to 12 carbon atoms; a fluoroalkyl substituted aryl comprising from 6 to 12 carbon atoms; a fluoroaryl comprising from 6 to 12 carbon atoms; an ether having a formula (CH 2 ) n O(C m H 2m+ 1) where n and m are independently a number ranging from 1 to 20; a fluoroether having a formula (C n H x F y )O(C m H w F z ) wherein (x+y)=2n, (w+z)=(2m+1), and n and m are each independently a number ranging from 1 to 20; a silylether having a formula (R 7 ) 3 SiO wherein R 7 is each independently an alkyl group comprising from 1 to 20 carbon atoms or an aryl group comprising from 6 to 12 carbon atoms; an alkoxy comprising from 1 to 20 carbon atoms; and an amide comprising from 1 to 20 carbon atoms and wherein R 4 associates with L by having a hydrogen, an atom, or a group removed;
wherein L is a ligand selected from an alkylnitrile comprising from 2 to 20 carbon atoms; a silylnitrile having the formula (R 8 ) 3 SiCN wherein R 8 is each independently an alkyl, an alkoxy, or an amide comprising from 1 to 20 carbon atoms; an alkyne comprising from 1 to 20 carbon atoms; a silylalkyne having a formula (R 9 ) 3 SiCCR 10 wherein R 9 is each independently an alkyl, an amide, or an alkoxy comprising from 1 to 20 carbon atoms and R 10 is hydrogen, an alkoxy, an amide, or an alkyl comprising from 1 to 20 carbon atoms; a silylalkyne having a formula (R 11 ) 3 SiCCSi(R 11 ) 3 wherein R 11 is each independently an alkyl, an amide, or an alkoxy comprising from 1 to 20 carbon atoms; an alkene, diene, or triene comprising from 1 to 20 carbon atoms; a silylalkene having a formula (R 12 ) 3 SiCR 13 C(R 13 ) 2 wherein R 12 is each independently an alkyl, an alkoxy, an aryl, a vinyl, or an amide comprising from 1 to 20 carbon atoms and R 13 is each independently a hydrogen, an alkyl comprising from 1 to 20 carbon atoms, or an aryl comprising from 6 to 12 carbon atoms; a bis(silyl)alkene having the formula (R 14 ) 3 SiCR 13 CR 13 Si(R 14 ) 3 wherein R 14 is each independently an alkyl, an alkoxy, or an amide comprising from 1 to 20 carbon atoms and R 13 is each independently a hydrogen atom or an alkyl comprising from 1 to 20 carbon atoms; an allene comprising from 3 to 20 carbons; an allene having a formula (R 15 ) 2 CCC(R 15 ) 2 where R 15 is each independently a hydrogen atom or an alkyl silane having a formula (R 16 ) 3 Si wherein R 16 is each independently an alkyl, an amide, or an alkoxy comprising from 1 to 20 carbon atoms; an alkylisocyanide having a formula R 17 NC wherein R 17 is an alkyl comprising from 1 to 20 carbon atoms; a silylisocyanide having a formula (R 18 ) 3 SiNC wherein R 18 is each independently an alkyl comprising from 1 to 20 carbon atoms; and an aryl group comprising from 6 to 12 carbon atoms and wherein L associates with R 4 by having a hydrogen, an atom, or a group removed; and
wherein an organometallic bond between M and L is selected from two single bonds or one single bond.
12. An electronic device comprising a film comprising copper wherein the film is deposited from a precursor mixture comprising a metal complex having formula (I):
wherein M is a metal selected from Cu, Au, Ag, Co, Ru, Rh, Pt, In, Pd, Ni, and Os;
wherein X is selected from oxygen and NR 5 ;
wherein R 1 , R 2 , R 3 , and R 5 are each independently selected from a hydrogen atom; a halogen atom; a nitro group having a formula NO 2 ; an alkyl having a formula C n H 2n+1 wherein n is a number ranging from 1 to 20; a fluoroalkyl having the formula C n H x F y wherein the product of the (x+y) equals the product of (2n+1) and n is a number ranging from 1 to 20; an alkylsilane having a formula (R 6 ) 3 Si wherein R 6 is each independently an alkyl, an alkoxy or an amide comprising from 1 to 20 carbon atoms; an aryl group comprising from 6 to 12 carbon atoms; an alkyl-substituted aryl comprising from 6 to 12 carbon atoms; a fluoroalkyl substituted aryl comprising from 6 to 12 carbon atoms; a fluoroaryl comprising from 6 to 12 carbon atoms; an ether having a formula (CH 2 ) n O(C m H 2m+1 ) where n and m are independently a number ranging from 1 to 20; a fluoroether having a formula (C n H x F y )O(C m H w F z ) wherein (x+y)=2n, (w+z)=(2m+1), and n and m are each independently a number ranging from 1 to 20; a silylether having a formula (R 7 ) 3 SiO wherein R 7 is each independently an alkyl comprising from 1 to 20 carbon atoms or an aryl comprising from 6 to 12 carbon atoms; an alkoxy comprising from 1 to 20 carbon atoms; and an amide comprising from 1 to 20 carbon atoms;
wherein R 4 is selected from an alkyl having a formula C n H 2n+1 wherein n is a number ranging from 1 to 20; a fluoroalkyl having the formula C n H x F y wherein the product of the (x+y) equals the product of (2n+1) and n is a number ranging from 1 to 20; an alkylsilane having a formula (R 6 ) 3 Si wherein R 6 is each independently an alkyl, an alkoxy or an amide comprising from 1 to 20 carbon atoms; an aryl comprising from 6 to 12 carbon atoms; an alkyl-substituted aryl comprising from 6 to 12 carbon atoms; a fluoroalkyl substituted aryl comprising from 6 to 12 carbon atoms; a fluoroaryl comprising from 6 to 12 carbon atoms; an ether having a formula (CH 2 ) n O(C m H 2m+1 ) where n and m are independently a number ranging from 1 to 20; a fluoroether having a formula (C n H x F y )O(C m H w F z ) wherein (x+y)=2n, (w+z)=(2m+1), and n and m are each independently a number ranging from 1 to 20; a silylether having a formula (R 7 ) 3 SiO wherein R 7 is each independently an alkyl group comprising from 1 to 20 carbon atoms or an aryl group comprising from 6 to 12 carbon atoms; an alkoxy comprising from 1 to 20 carbon atoms; and an amide comprising from 1 to 20 carbon atoms and wherein R 4 associates with L by having a hydrogen, an atom, or a group removed;
wherein L is a ligand selected from an alkylnitrile comprising from 2 to 20 carbon atoms; a silylnitrile having the formula (R 8 ) 3 SiCN wherein R 8 is each independently an alkyl, an alkoxy, or an amide comprising from 1 to 20 carbon atoms; an alkyne comprising from 1 to 20 carbon atoms; a silylalkyne having a formula (R 9 ) 3 SiCCR 10 wherein R 9 is each independently an alkyl, an amide, or an alkoxy comprising from 1 to 20 carbon atoms and R 10 is hydrogen, an alkoxy, an amide, or an alkyl comprising from 1 to 20 carbon atoms; a silylalkyne having a formula (R 11 ) 3 SiCCSi(R 11 ) 3 wherein R 11 is each independently an alkyl, an amide, or an alkoxy comprising from 1 to 20 carbon atoms; an alkene, diene, or triene comprising from 1 to 20 carbon atoms; a silylalkene having a formula (R 12 ) 3 SiCR 13 C(R 13 ) 2 wherein R 12 is each independently an alkyl, an alkoxy, an aryl, a vinyl, or an amide comprising from 1 to 20 carbon atoms and R 13 is each independently a hydrogen, an alkyl comprising from 1 to 20 carbon atoms, or an aryl comprising from 6 to 12 carbon atoms; a bis(silyl)alkene having the formula (R 14 ) 3 SiCR 13 CR 13 Si(R 14 ) 3 wherein R 14 is each independently an alkyl, an alkoxy, or an amide comprising from 1 to 20 carbon atoms and R 13 is each independently a hydrogen atom or an alkyl comprising from 1 to 20 carbon atoms; an allene comprising from 3 to 20 carbons; an allene having a formula (R 15 ) 2 CCC(R 15 ) 2 where R 15 is each independently a hydrogen atom or an alkyl silane having a formula (R 16 ) 3 Si wherein R 16 is each independently an alkyl, an amide, or an alkoxy comprising from 1 to 20 carbon atoms; an alkylisocyanide having a formula R 17 NC wherein R 17 is an alkyl comprising from 1 to 20 carbon atoms; a silylisocyanide having a formula (R 18 ) 3 SiNC wherein R 18 is each independently an alkyl comprising from 1 to 20 carbon atoms; and an aryl group comprising from 6 to 12 carbon atoms and wherein L associates with R 4 by having a hydrogen, an atom, or a group removed; and
wherein an organometallic bond between M and L is selected from two single bonds or one single bond.
13. A method of making a metal complex having formula (I):
wherein M is a metal selected from Cu, Au, Ag, Co, Ru, Rh, Pt, In, Pd, Ni, and Os;
wherein X is oxygen;
wherein R 1 , R 2 , and R 3 are each independently selected from a hydrogen atom; a halogen atom; a nitro group having a formula NO 2 ; an alkyl having a formula C n H 2n+1 wherein n is a number ranging from 1 to 20; a fluoroalkyl having the formula C n H x F y wherein the product of the (x+y) equals the product of (2n+1) and n is a number ranging from 1 to 20; an alkylsilane having a formula (R 6 ) 3 Si wherein R 6 is each independently an alkyl, an alkoxy or an amide comprising from 1 to 20 carbon atoms; an aWl group comprising from 6 to 12 carbon atoms; an alkyl-substituted aryl comprising from 6 to 12 carbon atoms; a fluoroalkyl substituted aryl comprising from 6 to 12 carbon atoms; a fluoroaryl comprising from 6 to 12 carbon atoms; an ether having a formula (CH 2 ) n O(C m H 2m+1 ) where n and m are independently a number ranging from 1 to 20; a fluoroether having a formula (C n H x F y )O(C m H w F z ) wherein (x+y)=2n, (w+z)=(2m+1), and n and m are each independently a number ranging from 1 to 20; a silylether having a formula (R 7 ) 3 SiO wherein R 7 is each independently an alkyl comprising from 1 to 20 carbon atoms or an aryl comprising from 6 to 12 carbon atoms; an alkoxy comprising from 1 to 20 carbon atoms; and an amide comprising from 1 to 20 carbon atoms;
wherein R 4 is selected from an alkyl having a formula C n H 2n+1 wherein n is a number ranging from 1 to 20; a fluoroalkyl having the formula C n H x F y wherein the product of the (x+y) equals the product of (2n+1) and n is a number ranging from 1 to 20; an alkylsilane having a formula (R 6 ) 3 Si wherein R 6 is each independently an alkyl, an alkoxy or an amide comprising from 1 to 20 carbon atoms; an aryl comprising from 6 to 12 carbon atoms; an alkyl-substituted aryl comprising from 6 to 12 carbon atoms; a fluoroalkyl substituted aryl comprising from 6 to 12 carbon atoms; a fluoroaryl comprising from 6 to 12 carbon atoms; an ether having a formula (CH 2 ) n O(C m H 2m+1 ) where n and m are independently a number ranging from 1 to 20; a fluoroether having a formula (C n H x F y )O(C m H w F z ) wherein (x+y)=2n, (w+z)=(2m+1), and n and m are each independently a number ranging from 1 to 20; a silylether having a formula (R 7 ) 3 SiO wherein R 7 is each independently an alkyl group comprising from 1 to 20 carbon atoms or an aryl group comprising from 6 to 12 carbon atoms; an alkoxy comprising from 1 to 20 carbon atoms; and an amide comprising from 1 to 20 carbon atoms and wherein R 4 associates with L by having a hydrogen, an atom, or a group removed;
wherein L is a ligand selected from an alkylnitrile comprising from 2 to 20 carbon atoms; a silylnitrile having the formula (R 8 ) 3 SiCN wherein R 8 is each independently an alkyl, an alkoxy, or an amide comprising from 1 to 20 carbon atoms; an alkyne comprising from 1 to 20 carbon atoms; a silylalkyne having a formula (R 9 ) 3 SiCCR 10 wherein R 9 is each independently an alkyl, an amide, or an alkoxy comprising from 1 to 20 carbon atoms and R 10 is hydrogen, an alkoxy, an amide, or an alkyl comprising from 1 to 20 carbon atoms; a silylalkyne having a formula (R 11 ) 3 SiCCSi(R 11 ) 3 wherein R 11 is each independently an alkyl, an amide, or an alkoxy comprising from 1 to 20 carbon atoms; an alkene, diene, or triene comprising from 1 to 20 carbon atoms; a silylalkene having a formula (R 12 ) 3 SiCR 13 C(R 13 ) 2 wherein R 12 is each independently an alkyl, an alkoxy, an aryl, a vinyl, or an amide comprising from 1 to 20 carbon atoms and R13 is each independently a hydrogen, an alkyl comprising from 1 to 20 carbon atoms, or an aryl comprising from 6 to 12 carbon atoms; a bis(silyl)alkene having the formula (R 14 ) 3 SiCR 13 CR 13 Si(R 14 ) 3 wherein R 14 is each independently an alkyl, an alkoxy, or an amide comprising from 1 to 20 carbon atoms and R 13 is each independently a hydrogen atom or an alkyl comprising from 1 to 20 carbon atoms; an allene comprising from 3 to 20 carbons; an allene having a formula (R 15 ) 2 CCC(R 15 ) 2 where R 15 is each independently a hydrogen atom or an alkyl silane having a formula (R 16 ) 3 Si wherein R 16 is each independently an alkyl, an amide, or an alkoxy comprising from 1 to 20 carbon atoms; an alkylisocyanide having a formula R 17 NC wherein R 17 is an alkyl comprising from 1 to 20 carbon atoms; a silylisocyanide having a formula (R 18 ) 3 SiNC wherein R 18 is each independently an alkyl comprising from 1 to 20 carbon atoms; and an aryl group comprising from 6 to 12 carbon atoms and wherein L associates with R 4 by having a hydrogen, an atom, or a group removed; and
wherein an organometallic bond between M and L is selected from two single bonds or one single bond, the method comprising:
providing a primary amine having a formula H 2 NR 4 L;
condensing the primary amine with a β-diketone compound having a formula R 1 C(O)CHR 2 C(O)R 3 to provide a β-ketoimine intermediate product having a formula R 1 C(O)CHR 2 CNR 4 LR 3 ; and
deprotonating the β-ketoimine intermediate product using a base in the presence of a metal source to form the metal complex.
14. A method of making a metal complex having formula (I):
wherein M is a metal selected from Cu, Au, Ag, Co, Ru, Rh, Pt, In, Pd, Ni, and Os;
wherein X is NR 5 ;
wherein R 1 , R 2 , R 3 , and R 5 are each independently selected from a hydrogen atom; a halogen atom; a nitro group having a formula NO 2 ; an alkyl having a formula C n H 2n+1 wherein n is a number ranging from 1 to 20; a fluoroalkyl having the formula C n H x F y wherein the product of the (x+y) equals the product of (2n+1) and n is a number ranging from 1 to 20; an alkylsilane having a formula (R 6 ) 3 Si wherein R 6 is each independently an alkyl, an alkoxy or an amide comprising from 1 to 20 carbon atoms; an aryl group comprising from 6 to 12 carbon atoms; an alkyl-substituted aryl comprising from 6 to 12 carbon atoms; a fluoroalkyl substituted aryl comprising from 6 to 12 carbon atoms; a fluoroaryl comprising from 6 to 12 carbon atoms; an ether having a formula (CH 2 ) n O(C m H 2m+1 ) where n and m are independently a number ranging from 1 to 20; a fluoroether having a formula (C n H x F y )O(C m H w F z ) wherein (x+y)=2n, (w+z)=(2m+1), and n and m are each independently a number ranging from 1 to 20; a silylether having a formula (R 7 ) 3 SiO wherein R 7 is each independently an alkyl comprising from 1 to 20 carbon atoms or an aryl comprising from 6 to 12 carbon atoms; an alkoxy comprising from 1 to 20 carbon atoms; and an amide comprising from 1 to 20 carbon atoms;
wherein R 4 is selected from an alkyl having a formula C n H 2n+1 wherein n is a number ranging from 1 to 20; a fluoroalkyl having the formula C n H x F y wherein the product of the (x+y) equals the product of (2n+1) and n is a number ranging from 1 to 20; an alkylsilane having a formula (R 6 ) 3 Si wherein R 6 is each independently an alkyl, an alkoxy or an amide comprising from 1 to 20 carbon atoms; an aryl comprising from 6 to 12 carbon atoms; an alkyl-substituted aryl comprising from 6 to 12 carbon atoms; a fluoroalkyl substituted aryl comprising from 6 to 12 carbon atoms; a fluoroaryl comprising from 6 to 12 carbon atoms; an ether having a formula (CH 2 ) n O(C m H 2m+1 ) where n and m are independently a number ranging from 1 to 20; a fluoroether having a formula (C n H x F y )O(C m H w F z ) wherein (x+y)=2n, (w+z)=(2m+1), and n and m are each independently a number ranging from 1 to 20; a silylether having a formula (R 7 ) 3 SiO wherein R 7 is each independently an alkyl group comprising from 1 to 20 carbon atoms or an aryl group comprising from 6 to 12 carbon atoms; an alkoxy comprising from 1 to 20 carbon atoms; and an amide comprising from 1 to 20 carbon atoms and wherein R 4 associates with L by having a hydrogen, an atom, or a group removed;
wherein L is a ligand selected from an alkylnitrile comprising from 2 to 20 carbon atoms; a silylnitrile having the formula (R 8 ) 3 SiCN wherein R 8 is each independently an alkyl, an alkoxy, or an amide comprising from 1 to 20 carbon atoms; an alkyne comprising from 1 to 20 carbon atoms; a silylalkyne having a formula (R 9 ) 3 SiCCR 10 wherein R 9 is each independently an alkyl, an amide, or an alkoxy comprising from 1 to 20 carbon atoms and R 10 is hydrogen, an alkoxy, an amide, or an alkyl comprising from 1 to 20 carbon atoms; a silylalkyne having a formula (R 11 ) 3 SiCCSi(R 11 ) 3 wherein R 11 is each independently an alkyl, an amide, or an alkoxy comprising from 1 to 20 carbon atoms; an alkene, diene, or triene comprising from 1 to 20 carbon atoms; a silylalkene having a formula (R 12 ) 3 SiCR 13 C(R 13 ) 2 wherein R 12 is each independently an alkyl, an alkoxy, an aryl, a vinyl, or an amide comprising from 1 to 20 carbon atoms and R 13 is each independently a hydrogen, an alkyl comprising from 1 to 20 carbon atoms, or an aryl comprising from 6 to 12 carbon atoms; a bis(silyl)alkene having the formula (R 14 ) 3 SiCR 13 CR 13 Si(R 14 ) 3 wherein R 14 is each independently an alkyl, an alkoxy, or an amide comprising from 1 to 20 carbon atoms and R 13 is each independently a hydrogen atom or an alkyl comprising from 1 to 20 carbon atoms; an allene comprising from 3 to 20 carbons; an allene having a formula (R 15 ) 2 CCC(R 15 ) 2 where R 15 is each independently a hydrogen atom or an alkyl silane having a formula (R 16 ) 3 Si wherein R 16 is each independently an alkyl, an amide, or an alkoxy comprising from 1 to 20 carbon atoms; an alkylisocyanide having a formula R 17 NC wherein R 17 is an alkyl comprising from 1 to 20 carbon atoms; a silylisocyanide having a formula (R 18 ) 3 SiNC wherein R 18 is each independently an alkyl comprising from 1 to 20 carbon atoms; and an aryl group comprising from 6 to 12 carbon atoms and wherein L associates with R 4 by having a hydrogen, an atom, or a group removed; and
wherein an organometallic bond between M and L is selected from two single bonds or one single bond, the method comprising:
providing a primary amine having a formula H 2 NR 4 L;
reacting the primary amine with a β-diketone compound having a formula R 1 C(O)CHR 2 C(O)R 3 to provide a β-ketoimine intermediate product having a formula R 1 C(O)CHR 2 CN(R 4 )(L)R 3 ; and
treating the β-ketoimine intermediate product within an alkylating agent and reacting with R 5 NH 2 to provide a salt having a formula R 1 C(R 5 NH)CHR 2 C(NR 4 L)R 3 ] + [V] − where V is a conjugate base of the alkylating agent; and
deprotonating the β-ketoimine intermediate product a plurality of times using a base in the presence of a metal source to form the metal complex.
15. A method of making a metal complex having formula (I):
wherein M is a metal selected from Cu, Au, Ag, Co, Ru, Rh, Pt, In, Pd, Ni, and Os;
wherein X is oxygen;
wherein R 1 , R 2 , and R 3 are each independently selected from a hydrogen atom; a halogen atom; a nitro group having a formula NO 2 ; an alkyl having a formula C n H 2n+1 wherein n is a number ranging from 1 to 20; a fluoroalkyl having the formula C n H x F y wherein the product of the (x+y) equals the product of (2n+1) and n is a number ranging from 1 to 20; an alkylsilane having a formula (R 6 ) 3 Si wherein R 6 is each independently an alkyl, an alkoxy or an amide comprising from 1 to 20 carbon atoms; an aryl group comprising from 6 to 12 carbon atoms; an alkyl-substituted aryl comprising from 6 to 12 carbon atoms; a fluoroalkyl substituted aryl comprising from 6 to 12 carbon atoms; a fluoroaryl comprising from 6 to 12 carbon atoms; an ether having a formula (CH 2 ) n O(C m H 2m+1 ) where n and m are independently a number ranging from 1 to 20; a fluoroether having a formula (C n H x F y )O(C m H w F z ) wherein (x+y)=2n, (w+z)=(2m+1), and n and m are each independently a number ranging from 1 to 20; a silylether having a formula (R 7 ) 3 SiO wherein R 7 is each independently an alkyl comprising from 1 to 20 carbon atoms or an aryl comprising from 6 to 12 carbon atoms; an alkoxy comprising from 1 to 20 carbon atoms; and an amide comprising from 1 to 20 carbon atoms;
wherein R 4 is selected from an alkyl having a formula C n H 2n+1 wherein n is a number ranging from 1 to 20; a fluoroalkyl having the formula C n H x F y wherein the product of the (x+y) equals the product of (2n+1) and n is a number ranging from 1 to 20; an alkylsilane having a formula (R 6 ) 3 Si wherein R 6 is each independently an alkyl, an alkoxy or an amide comprising from 1 to 20 carbon atoms; an aryl comprising from 6 to 12 carbon atoms; an alkyl-substituted aryl comprising from 6 to 12 carbon atoms; a fluoroalkyl substituted aryl comprising from 6 to 12 carbon atoms; a fluoroaryl comprising from 6 to 12 carbon atoms; an ether having a formula (CH 2 ) n O(C m H 2m+1 ) where n and m are independently a number ranging from 1 to 20; a fluoroether having a formula (C n H x F y )O(C m H w F z ) wherein (x+y)=2n, (w+z)=(2m+1), and n and m are each independently a number ranging from 1 to 20; a silylether having a formula (R 7 ) 3 SiO wherein R 7 is each independently an alkyl group comprising from 1 to 20 carbon atoms or an aryl group comprising from 6 to 12 carbon atoms; an alkoxy comprising from 1 to 20 carbon atoms; and an amide comprising from 1 to 20 carbon atoms and wherein R 4 associates with L by having a hydrogen, an atom, or a group removed;
wherein L is a ligand selected from an alkylnitrile comprising from 2 to 20 carbon atoms; a silylnitrile having the formula (R 8 ) 3 SiCN wherein R 8 is each independently an alkyl, an alkoxy, or an amide comprising from 1 to 20 carbon atoms; an alkyne comprising from 1 to 20 carbon atoms; a silylalkyne having a formula (R 9 ) 3 SiCCR 10 wherein R 9 is each independently an alkyl, an amide, or an alkoxy comprising from 1 to 20 carbon atoms and R 10 is hydrogen, an alkoxy, an amide, or an alkyl comprising from 1 to 20 carbon atoms; a silylalkyne having a formula (R 11 ) 3 SiCCSi(R 11 ) 3 wherein R 11 is each independently an alkyl, an amide, or an alkoxy comprising from 1 to 20 carbon atoms; an alkene, diene, or triene comprising from 1 to 20 carbon atoms; a silylalkene having a formula (R 12 ) 3 SiCR 13 C(R 13 ) 2 wherein R 12 is each independently an alkyl, an alkoxy, an aryl, a vinyl, or an amide comprising from 1 to 20 carbon atoms and R 13 is each independently a hydrogen, an alkyl comprising from 1 to 20 carbon atoms, or an aryl comprising from 6 to 12 carbon atoms; a bis(silyl)alkene having the formula (R 14 ) 3 SiCR 13 CR 13 Si(R 14 ) 3 wherein R 14 is each independently an alkyl, an alkoxy, or an amide comprising from 1 to 20 carbon atoms and R 13 is each independently a hydrogen atom or an alkyl comprising from 1 to 20 carbon atoms; an allene comprising from 3 to 20 carbons; an allene having a formula (R 15 ) 2 CCC(R 15 ) 2 where R 15 is each independently a hydrogen atom or an alkyl silane having a formula (R 16 ) 3 Si wherein R 16 is each independently an alkyl, an amide, or an alkoxy comprising from 1 to 20 carbon atoms; an alkylisocyanide having a formula R 17 NC wherein R 17 is an alkyl comprising from 1 to 20 carbon atoms; a silylisocyanide having a formula (R 18 ) 3 SiNC wherein R 18 is each independently an alkyl comprising from 1 to 20 carbon atoms; and an aryl group comprising from 6 to 12 carbon atoms and wherein L associates with R 4 by having a hydrogen, an atom, or a group removed; and
wherein an organometallic bond between M and L is selected from two single bonds or one single bond, the method comprising:
providing a primary amine having a formula H 2 NR 4 ;
condensing the primary amine with a β-diketone compound having a formula R 1 C(O)CHR 2 C(O)R 3 to provide a first β-ketoimine intermediate product having a formula R 1 C(O)CHR 2 CN(R 4 )R 3 ;
attaching ligand (L) to the first β-ketoimine intermediate product to provide a second intermediate product having a formula R 1 C(O)CHR 2 CN(R 4 )LR 3 ; and
deprotonating the second β-ketoimine intermediate product using a base in the presence of a metal source to form the metal complex.
16. Cu(MeC(O)CHC(NCH 2 CH 2 OSiMe 2 (C 2 H 3 ))Me).
17. Cu(MeC(O)CHC(NCH 2 CH 2 NSiMe 2 (C 2 H 3 ))Me).
18. A metal complex represented by a following formula:
wherein X is selected from oxygen and NR 5 ;
wherein R 1 , R 2 , R 3 , and R 5 are each independently selected from a hydrogen atom; a halogen atom; a nitro group having a formula NO 2 ; an alkyl having a formula C n H 2n+1 wherein n is a number ranging from 1 to 20; a fluoroalkyl having the formula C n H x F y wherein the product of the (x+y) equals the product of (2n+1) and n is a number ranging from 1 to 20; an alkylsilane having a formula (R 6 ) 3 Si wherein R 6 is each independently an alkyl, an alkoxy or an amide comprising from 1 to 20 carbon atoms; an aryl group comprising from 6 to 12 carbon atoms; an alkyl-substituted aryl comprising from 6 to 12 carbon atoms; a fluoroalkyl substituted aryl comprising from 6 to 12 carbon atoms; a fluoroaryl comprising from 6 to 12 carbon atoms; an ether having a formula (CH 2 ) n O(C m H 2m+1 ) where n and m are independently a number ranging from 1 to 20; a fluoroether having a formula (C n H x F y )O(C m H w F z ) wherein (x+y)=2n, (w+z)=(2m+1), and n and m are each independently a number ranging from 1 to 20; a silylether having a formula (R 7 ) 3 SiO wherein R 7 is each independently an alkyl comprising from 1 to 20 carbon atoms or an aryl comprising from 6 to 12 carbon atoms; an alkoxy comprising from 1 to 20 carbon atoms; and an amide comprising from 1 to 20 carbon atoms;
wherein R 4 is selected from an alkyl having a formula C n H 2n+1 wherein n is a number ranging from 1 to 20; a fluoroalkyl having the formula C n H x F y wherein the product of the (x+y) equals the product of (2n+1) and n is a number ranging from 1 to 20; an alkylsilane having a formula (R 6 ) 3 Si wherein R 6 is each independently an alkyl, an alkoxy or an amide comprising from 1 to 20 carbon atoms; an aryl comprising from 6 to 12 carbon atoms; an alkyl-substituted aryl comprising from 6 to 12 carbon atoms; a fluoroalkyl substituted aryl comprising from 6 to 12 carbon atoms; a fluoroaryl comprising from 6 to 12 carbon atoms; an ether having a formula (CH 2 ) n O(C m H 2m+1 ) where n and m are independently a number ranging from 1 to 20; a fluoroether having a formula (C n H x F y )O(C m H w F z ) wherein (x+y)=2n, (w+z)=(2m+1), and n and m are each independently a number ranging from 1 to 20; a silylether having a formula (R 7 ) 3 SiO wherein R 7 is each independently an alkyl group comprising from 1 to 20 carbon atoms or an aryl group comprising from 6 to 12 carbon atoms; an alkoxy comprising from 1 to 20 carbon atoms; and an amide comprising from 1 to 20 carbon atoms and wherein R 4 associates with L by having a hydrogen, an atom, or a group removed;
wherein L is a ligand selected from an alkylnitrile comprising from 2 to 20 carbon atoms; a silylnitrile having the formula (R 8 ) 3 SiCN wherein R 8 is each independently an alkyl, an alkoxy, or an amide comprising from 1 to 20 carbon atoms; an alkyne comprising from 1 to 20 carbon atoms; a silylalkyne having a formula (R 9 ) 3 SiCCR 10 wherein R 9 is each independently an alkyl, an amide, or an alkoxy comprising from 1 to 20 carbon atoms and R 10 is hydrogen, an alkoxy, an amide, or an alkyl comprising from 1 to 20 carbon atoms; a silylalkyne having a formula (R 11 ) 3 SiCCSi(R 11 ) 3 wherein R 11 is each independently an alkyl, an amide, or an alkoxy comprising from 1 to 20 carbon atoms; an alkene, diene, or triene comprising from 1 to 20 carbon atoms; a silylalkene having a formula (R 12 ) 3 SiCR 13 (R 13 ) 2 wherein R 12 is each independently an alkyl, an alkoxy, an aryl, a vinyl, or an amide comprising from 1 to 20 carbon atoms and R 13 is each independently a hydrogen, an alkyl comprising from 1 to 20 carbon atoms, or an aryl comprising from 6 to 12 carbon atoms; a bis(silyl)alkene having the formula (R 14 ) 3 SiCR 13 CR 13 Si(R 14 ) 3 wherein R 14 is each independently an alkyl, an alkoxy, or an amide comprising from 1 to 20 carbon atoms and R 13 is each independently a hydrogen atom or an alkyl comprising from 1 to 20 carbon atoms; an allene comprising from 3 to 20 carbons; an allene having a formula (R 15 ) 2 CCC(R 15 ) 2 where R 15 is each independently a hydrogen atom or an alkyl silane having a formula (R 16 ) 3 Si wherein R 16 is each independently an alkyl, an amide, or an alkoxy comprising from 1 to 20 carbon atoms; an alkylisocyanide having a formula R 17 NC wherein R 17 is an alkyl comprising from 1 to 20 carbon atoms; a silylisocyanide having a formula (R 18 ) 3 SiNC wherein R 18 is each independently an alkyl comprising from 1 to 20 carbon atoms; and an aryl group comprising from 6 to 12 carbon atoms and wherein L associates with R 4 by having a hydrogen, an atom, or a group removed; and
wherein an organometallic bond between M and L is selected from two single bonds or one single bond.