Granted Patent B2

US 7,964,746 · App. 12/058,751 · Granted Jun 21, 2011

Abstract

Claims (68)

1. A copper precursor composition comprising: a compound selected from the group consisting of compounds of formulae (i)-(viii):

wherein each of R 1 , R 2 , R 3 , R 4 and R 5 may be the same as or different from the others, and each is independently selected from among hydrogen, C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 6 -C 10 aryl, C 1 -C 6 alkoxy, C 3 -C 6 alkylsilyl, C 1 -C 6 amino, hydrazino of the formula R a R b NNR c — wherein each of R a , R b and R a may be the same as or different from one another and each is independently selected from among C 1 -C 6 alkyl, and pendant ligands including functional group(s) providing further coordination to the metal center, selected from the group consisting of aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, and groups of the following formulae:

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen and C 1 -C 6 straight chain or branched alkyl, C 1 -C 6 straight chain or branched alkoxy, C 6 -C 10 aryl and NR 5 R 6 ; each of R 5 and R 6 is the same as or different from the other, with each being independently selected from among C 1 -C 6 straight chain or branched alkyl and C 6 -C 10 aryl; n and m are each selected independently from 0 to 4 with the proviso that m and n cannot be 0 at the same time, and x is selected from 1 to 5;

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen, C 1 -C 6 alkyl, and C 6 -C 10 aryl; R 5 is selected from among C 1 -C 6 alkyl, and C 6 -C 10 aryl; and n and m are selected independently from 0 to 4, with the proviso that m and n cannot be 0 at the same time; each L may be the same as or different from the other, each is a unidentate or multidentate Lewis-base ligand, and each is independently selected from the group consisting of phosphines, tertiary phosphines, ethers, polyethers, amines, alkylamines, polyamines, glymes, crown ethers, crown thioethers, cyclic polyamines (cyclenes), thioglymes, C 2 -C 6 alkynes, azoles, imidazoles, C 2 -C 6 alkenes, pyridines, bipyridines, isonitriles, carbenes and hetero-carbenes;

wherein each of R 1 , R 2 , R 3 , R 4 and R 5 may be the same as or different from the others, and each is independently selected from among hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 6 -C 10 aryl, C 1 -C 6 alkoxy, C 3 -C 6 alkylsilyl, C 1 -C 6 amino, hydrazino of the formula R a R b NNR c — wherein each of R a , R b and R c may be the same as or different from one another and each is independently selected from among C 1 -C 6 alkyl, and pendant ligands including functional group(s) providing further coordination to the metal center, selected from the group consisting of aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, and groups of the following formulae:

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen and C 1 -C 6 straight chain or branched alkyl, C 1 -C 6 straight chain or branched alkoxy, C 6 -C 10 aryl and NR 5 R 6 ; each of R 5 and R 6 is the same as or different from the other, with each being independently selected from among C 1 -C 6 straight chain or branched alkyl and C 6 -C 10 aryl; n and m are each selected independently from 0 to 4 with the proviso that m and n cannot be 0 at the same time, and x is selected from 1 to 5;

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen, C 1 -C 6 alkyl, and C 6 -C 10 aryl; R 5 is selected from among C 1 -C 6 alkyl, and C 6 -C 10 aryl; and n and m are selected independently from 0 to 4, with the proviso that m and n cannot be 0 at the same time;

wherein each of R 1 , R 2 , R 3 , R 4 and R 5 may be the same as or different from the others, and each is independently selected from among hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 6 -C 10 aryl, C 1 -C 6 alkoxy, C 3 -C 6 alkylsilyl, C 1 -C 6 amino, hydrazino of the formula R a R b NNR c — wherein each of R a , R b and R c may be the same as or different from one another and each is independently selected from among C 1 -C 6 alkyl, and pendant ligands including functional group(s) providing further coordination to the metal center, selected from the group consisting of aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, and groups of the following formulae:

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen and C 1 -C 6 straight chain or branched alkyl, C 1 -C 6 straight chain or branched alkoxy, C 6 -C 10 aryl and NR 5 R 6 ; each of R 5 and R 6 is the same as or different from the other, with each being independently selected from among C 1 -C 6 straight chain or branched alkyl and C 6 -C 10 aryl; n and m are each selected independently from 0 to 4 with the proviso that m and n cannot be 0 at the same time, and x is selected from 1 to 5;

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen, C 1 -C 6 alkyl, and C 6 -C 10 aryl; R 5 is selected from among C 1 -C 6 alkyl, and C 6 -C 10 aryl; and n and m are selected independently from 0 to 4, with the proviso that m and n cannot be 0 at the same time; each L may be the same as or different from the other, each is a unidentate or multidentate Lewis-base ligand, and each is independently selected from the group consisting of phosphines, tertiary phosphines, ethers, polyethers, amines, alkylamines, polyamines, glymes, crown ethers, crown thioethers, cyclic polyamines (cyclenes), thioglymes, C 2 -C 6 alkynes, azoles, imidazoles, C 2 -C 6 alkenes, pyridines, bipyridines, isonitriles, carbenes and hetero-carbenes;

wherein each of R 1 , R 2 , R 3 , R 4 and R 5 may be the same as or different from the others, and each is independently selected from among hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 6 -C 10 aryl, C 1 -C 6 alkoxy, C 3 -C 6 alkylsilyl, C 1 -C 6 amino, hydrazino of the formula R a R b NNR c — wherein each of R a , R b and R c may be the same as or different from one another and each is independently selected from among C 1 -C 6 alkyl, and pendant ligands including functional group(s) providing further coordination to the metal center, selected from the group consisting of aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, and groups of the following formulae:

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen and C 1 -C 6 straight chain or branched alkyl, C 1 -C 6 straight chain or branched alkoxy, C 6 -C 10 aryl and NR 5 R 6 ; each of R 5 and R 6 is the same as or different from the other, with each being independently selected from among C 1 -C 6 straight chain or branched alkyl and C 6 -C 10 aryl; n and m are each selected independently from 0 to 4 with the proviso that m and n cannot be 0 at the same time, and x is selected from 1 to 5;

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen, C 1 -C 6 alkyl, and C 6 -C 10 aryl; R 5 is selected from among C 1 -C 6 alkyl, and C 6 -C 10 aryl; and n and m are selected independently from 0 to 4, with the proviso that m and n cannot be 0 at the same time;

wherein each of R 1 , R 2 , R 3 , R 4 and R 5 may be the same as or different from the others, and each is independently selected from among hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 6 -C 10 aryl, C 1 -C 6 alkoxy, C 3 -C 6 alkylsilyl, C 1 -C 6 amino, hydrazino of the formula R a R b NNR c — wherein each of R a , R b and R c may be the same as or different from one another and each is independently selected from among C 1 -C 6 alkyl, and pendant ligands including functional group(s) providing further coordination to the metal center, selected from the group consisting of aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, and groups of the following formulae:

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen and C 1 -C 6 straight chain or branched alkyl, C 1 -C 6 straight chain or branched alkoxy, C 6 -C 10 aryl and NR 5 R 6 ; each of R 5 and R 6 is the same as or different from the other, with each being independently selected from among C 1 -C 6 straight chain or branched alkyl and C 6 -C 10 aryl; n and m are each selected independently from 0 to 4 with the proviso that m and n cannot be 0 at the same time, and x is selected from 1 to 5;

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen, C 1 -C 6 alkyl, and C 6 -C 10 aryl; R 5 is selected from among C 1 -C 6 alkyl, and C 6 -C 10 aryl; and n and m are selected independently from 0 to 4, with the proviso that m and n cannot be 0 at the same time; each L may be the same as or different from the other, each is a unidentate or multidentate Lewis-base ligand, and each is independently selected from the group consisting of phosphines, tertiary phosphines, ethers, polyethers, amines, alkylamines, polyamines, glymes, crown ethers, crown thioethers, cyclic polyamines (cyclenes), thioglymes, C 2 -C 6 alkynes, azoles, imidazoles, C 2 -C 6 alkenes, pyridines, bipyridines, isonitriles, carbenes and hetero-carbenes;

wherein each of R 1 , R 2 , R 3 , R 4 and R 5 may be the same as or different from the others, and each is independently selected from among hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 6 -C 10 aryl, C 1 -C 6 alkoxy, C 3 -C 6 alkylsilyl, C 1 -C 6 amino, hydrazino of the formula R a R b NNR c — wherein each of R a , R b and R c may be the same as or different from one another and each is independently selected from among C 1 -C 6 alkyl, and pendant ligands including functional group(s) providing further coordination to the metal center, selected from the group consisting of aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, and groups of the following formulae:

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen and C 1 -C 6 straight chain or branched alkyl, C 1 -C 6 straight chain or branched alkoxy, C 6 -C 10 aryl and NR 5 R 6 ; each of R 5 and R 6 is the same as or different from the other, with each being independently selected from among C 1 -C 6 straight chain or branched alkyl and C 6 -C 10 aryl; n and m are each selected independently from 0 to 4 with the proviso that m and n cannot be 0 at the same time, and x is selected from 1 to 5;

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen, C 1 -C 6 alkyl, and C 6 -C 10 aryl; R 5 is selected from among C 1 -C 6 alkyl, and C 6 -C 10 aryl; and n and m are selected independently from 0 to 4, with the proviso that m and n cannot be 0 at the same time;

wherein each of R 1 , R 2 , R 3 , R 4 and R 5 may be the same as or different from the others, and each is independently selected from among hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 6 -C 10 aryl, C 1 -C 6 alkoxy, C 3 -C 6 alkylsilyl, C 1 -C 6 amino, hydrazino of the formula R a R b NNR c — wherein each of R a , R b and R c may be the same as or different from one another and each is independently selected from among C 1 -C 6 alkyl, and pendant ligands including functional group(s) providing further coordination to the metal center, selected from the group consisting of aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, and groups of the following formulae:

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen and C 1 -C 6 straight chain or branched alkyl, C 1 -C 6 straight chain or branched alkoxy, C 6 -C 10 aryl and NR 5 R 6 ; each of R 5 and R 6 is the same as or different from the other, with each being independently selected from among C 1 -C 6 straight chain or branched alkyl and C 6 -C 10 aryl; n and m are each selected independently from 0 to 4 with the proviso that m and n cannot be 0 at the same time, and x is selected from 1 to 5;

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen, C 1 -C 6 alkyl, and C 6 -C 10 aryl; R 5 is selected from among C 1 -C 6 alkyl, and C 6 -C 10 aryl; and n and m are selected independently from 0 to 4, with the proviso that m and n cannot be 0 at the same time; L is a unidentate or multidentate Lewis-base ligand selected from the group consisting of phosphines, tertiary phosphines, ethers, polyethers, amines, alkylamines, polyamines, glymes, crown ethers, crown thioethers, cyclic polyamines (cyclenes), thioglymes, C 2 -C 6 alkynes, azoles, imidazoles, C 2 -C 6 alkenes, pyridines, bipyridines, isonitriles, carbenes and hetero-carbenes;

wherein each of R 1 , R 2 , R 3 , R 4 and R 5 may be the same as or different from the others, and each is independently selected from among hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 6 -C 10 aryl, C 1 -C 6 alkoxy, C 3 -C 6 alkylsilyl, C 1 -C 6 amino, hydrazino of the formula R a R b NNR c — wherein each of R a , R b and R c may be the same as or different from one another and each is independently selected from among C 1 -C 6 alkyl, and pendant ligands including functional group(s) providing further coordination to the metal center, selected from the group consisting of aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, and groups of the following formulae:

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen and C 1 -C 6 straight chain or branched alkyl, C 1 -C 6 straight chain or branched alkoxy, C 6 -C 10 aryl and NR 5 R 6 ; each of R 5 and R 6 is the same as or different from the other, with each being independently selected from among C 1 -C 6 straight chain or branched alkyl and C 6 -C 10 aryl; n and m are each selected independently from 0 to 4 with the proviso that m and n cannot be 0 at the same time, and x is selected from 1 to 5;

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen, C 1 -C 6 alkyl, and C 6 -C 10 aryl; R 5 is selected from among C 1 -C 6 alkyl, and C 6 -C 10 aryl; and n and m are selected independently from 0 to 4, with the proviso that m and n cannot be 0 at the same time;

and a solvent medium.

2. The copper precursor formulation of claim 1 , wherein the solvent medium comprises a solvent selected from the group consisting of alkane solvents, hexane, heptane, octane, pentane, aryl solvents, benzene, toluene, amines, triethylamine, tert-butylamine, imines, carbodiimides, N,N′-diisopropylcarbodiimide, alcohols, ethers, ketones, aldehydes, amidines, guanadines, and isoureas.

3. A precursor vapor composition, comprising a vapor of a copper precursor composition of claim 1 .

4. A reagent source package, comprising a storage and dispensing vessel containing a copper precursor composition of claim 1 .

5. A method of making a cyclopentadienyl-type copper precursor, comprising carrying out a synthesis process comprising a synthetic route selected from the group consisting of:

(I) the synthetic route comprising

wherein L is a unidentate or multidentate Lewis-base ligand selected from the group consisting of phosphines, tertiary phosphines, ethers, polyethers, amines, alkylamines, polyamines, glymes, crown ethers, crown thioethers, cyclic polyamines (cyclenes), thioglymes, C 2 -C 6 alkynes, azoles, imidazoles, C 2 -C 6 alkenes, pyridines, bipyridines, isonitriles, carbenes and hetero-carbenes; and

(II) the synthetic route corresponding to synthetic route (I) wherein cyclopentadienyl substituents instead of being all methyl are each independently selected from among hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 6 -C 10 aryl, C 1 -C 6 alkoxy, C 3 -C 6 alkylsilyl, C 1 -C 6 amino, hydrazino of the formula R a R b NNR c — wherein each of R a , R b and R c may be the same as or different from one another and each is independently selected from among C 1 -C 6 alkyl, and pendant ligands including functional group(s) providing further coordination to the metal center, such as, for example, aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, wherein suitable groups in these classes include those of the following formulae:

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen and C 1 -C 6 straight chain or branched alkyl, C 1 -C 6 straight chain or branched alkoxy, C 6 -C 10 aryl and NR 5 R 6 ; each of R 5 and R 6 is the same as or different from the other, with each being independently selected from among C 1 -C 6 straight chain or branched alkyl and C 6 -C 10 aryl; n and m are each selected independently from 0 to 4 with the proviso that m and n cannot be 0 at the same time, and x is selected from 1 to 5;

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen, C 1 -C 6 alkyl, and C 6 -C 10 aryl; R 5 is selected from among C 1 -C 6 alkyl, and C 6 -C 10 aryl; and n and m are selected independently from 0 to 4, with the proviso that m and n cannot be 0 at the same time; and with L being a unidentate or multidentate Lewis-base ligand selected from the group consisting of phosphines, tertiary phosphines, ethers, polyethers, amines, alkylamines, polyamines, glymes, crown ethers, crown thioethers, cyclic polyamines (cyclenes), thioglymes, C 2 -C 6 alkynes, azoles, imidazoles, C 2 -C 6 alkenes, pyridines, bipyridines, isonitriles, carbenes and hetero-carbenes; and recovering said cyclopentadienyl-type copper precursor from a reaction volume including reactants and products of said synthesis.

6. A copper precursor compound selected from the group consisting of CpCu(CyNC), EtCpCu(tBuNC), and MeCpCu(tBuNC), wherein Cp is cyclopentadienyl, Cy is cyclohexyl, Et is ethyl, and tBu is tertiary butyl.

7. The copper precursor compound of claim 6 , comprising CpCu(CyNC).

8. The copper precursor compound of claim 6 , comprising EtCpCu(tBuNC).

9. The copper precursor compound of claim 6 , comprising MeCpCu(tBuNC).

10. A copper precursor formulation comprising a copper precursor compound of claim 6 and a solvent medium.

11. The copper precursor formulation of claim 10 , wherein the solvent medium comprises a solvent selected from the group consisting of alkane solvents, hexane, heptane, octane, pentane, aryl solvents, benzene, toluene, amines, triethylamine, tert-butylamine, imines, carbodiimides, N,N′-diisopropylcarbodiimide, alcohols, ethers, ketones, aldehydes, amidines, guanadines, and isoureas.

12. A precursor vapor composition, comprising a vapor of a copper precursor compound of claim 6 .

13. A reagent source package, comprising a storage and dispensing vessel containing a copper precursor compound of claim 6 .

14. A copper precursor compound selected from the group consisting of compounds of formulae (i)-(viii):

wherein each of R 1 , R 2 , R 3 , R 4 and R 5 may be the same as or different from the others, and each is independently selected from among hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 6 -C 10 aryl, C 1 -C 6 alkoxy, C 3 -C 6 alkylsilyl, C 1 -C 6 amino, hydrazino of the formula R a R b NNR c — wherein each of R a , R b and R c may be the same as or different from one another and each is independently selected from among C 1 -C 6 alkyl, and pendant ligands including functional group(s) providing further coordination to the metal center, selected from the group consisting of aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, and groups of the following formulae:

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen and C 1 -C 6 straight chain or branched alkyl, C 1 -C 6 straight chain or branched alkoxy, C 6 -C 10 aryl and NR 5 R 6 ; each of R 5 and R 6 is the same as or different from the other, with each being independently selected from among C 1 -C 6 straight chain or branched alkyl and C 6 -C 10 aryl; n and m are each selected independently from 0 to 4 with the proviso that m and n cannot be 0 at the same time, and x is selected from 1 to 5;

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen, C 1 -C 6 alkyl, and C 6 -C 10 aryl; R 5 is selected from among C 1 -C 6 alkyl, and C 6 -C 10 aryl; and n and m are selected independently from 0 to 4, with the proviso that m and n cannot be 0 at the same time; each L may be the same as or different from the other, each is a unidentate or multidentate Lewis-base ligand, and each is independently selected from the group consisting of ethers, polyethers, amines, alkylamines, polyamines, glymes, crown ethers, crown thioethers, cyclic polyamines (cyclenes), thioglymes, C 2 -C 6 alkynes, azoles, imidazoles, pyridines, bipyridines, and isonitriles;

wherein each of R 1 , R 2 , R 3 , R 4 and R 5 may be the same as or different from the others, and each is independently selected from among C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 6 -C 10 aryl, C 1 -C 6 alkoxy, C 3 -C 6 alkylsilyl, C 1 -C 6 amino, hydrazino of the formula R a R b NNR c — wherein each of R a , R b and R c may be the same as or different from one another and each is independently selected from among C 1 -C 6 alkyl, and pendant ligands including functional group(s) providing further coordination to the metal center, selected from the group consisting of aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, and groups of the following formulae:

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen and C 1 -C 6 straight chain or branched alkyl, C 1 -C 6 straight chain or branched alkoxy, C 6 -C 10 aryl and NR 5 R 6 ; each of R 5 and R 6 is the same as or different from the other, with each being independently selected from among C 1 -C 6 straight chain or branched alkyl and C 6 -C 10 aryl; n and m are each selected independently from 0 to 4 with the proviso that m and n cannot be 0 at the same time, and x is selected from 1 to 5;

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen, C 1 -C 6 alkyl, and C 6 -C 10 aryl; R 5 is selected from among C 1 -C 6 alkyl, and C 6 -C 10 aryl; and n and m are selected independently from 0 to 4, with the proviso that m and n cannot be 0 at the same time;

wherein each of R 1 , R 2 , R 3 , R 4 and R 5 may be the same as or different from the others, and each is independently selected from among hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 6 -C 10 aryl, C 1 -C 6 alkoxy, C 3 -C 6 alkylsilyl, C 1 -C 6 amino, hydrazino of the formula R a R b NNR c — wherein each of R a , R b and R c may be the same as or different from one another and each is independently selected from among C 1 -C 6 alkyl, and pendant ligands including functional group(s) providing further coordination to the metal center, selected from the group consisting of aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, and groups of the following formulae:

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen and C 1 -C 6 straight chain or branched alkyl, C 1 -C 6 straight chain or branched alkoxy, C 6 -C 10 aryl and NR 5 R 6 ; each of R 5 and R 6 is the same as or different from the other, with each being independently selected from among C 1 -C 6 straight chain or branched alkyl and C 6 -C 10 aryl; n and m are each selected independently from 0 to 4 with the proviso that m and n cannot be 0 at the same time, and x is selected from 1 to 5;

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen, C 1 -C 6 alkyl, and C 6 -C 10 aryl; R 5 is selected from among C 1 -C 6 alkyl, and C 6 -C 10 aryl; and n and m are selected independently from 0 to 4, with the proviso that m and n cannot be 0 at the same time; each L may be the same as or different from the other, each is a unidentate or multidentate Lewis-base ligand, and each is independently selected from the group consisting of ethers, polyethers, amines, alkylamines, polyamines, glymes, crown ethers, crown thioethers, cyclic polyamines (cyclenes), thioglymes, C 2 -C 6 alkynes, azoles, imidazoles, pyridines, bipyridines, and isonitriles;

wherein each of R 1 , R 2 , R 3 , R 4 and R 5 may be the same as or different from the others, and each is independently selected from among hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 6 -C 10 aryl, C 1 -C 6 alkoxy, C 3 -C 6 alkylsilyl, C 1 -C 6 amino, hydrazino of the formula R a R b NNR c — wherein each of R a , R b and R c may be the same as or different from one another and each is independently selected from among C 1 -C 6 alkyl, and pendant ligands including functional group(s) providing further coordination to the metal center, selected from the group consisting of aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, and groups of the following formulae:

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen and C 1 -C 6 straight chain or branched alkyl, C 1 -C 6 straight chain or branched alkoxy, C 6 -C 10 aryl and NR 5 R 6 ; each of R 5 and R 6 is the same as or different from the other, with each being independently selected from among C 1 -C 6 straight chain or branched alkyl and C 6 -C 10 aryl; n and m are each selected independently from 0 to 4 with the proviso that m and n cannot be 0 at the same time, and x is selected from 1 to 5;

wherein each of R 1 -R 4 is the same as or, different from one another, with each being independently selected from among hydrogen, C 1 -C 6 alkyl, and C 6 -C 10 aryl; R 5 is selected from among C 1 -C 6 alkyl, and C 6 -C 10 aryl; and n and m are selected independently from 0 to 4, with the proviso that m and n cannot be 0 at the same time;

wherein each of R 1 , R 2 , R 3 , R 4 and R 5 may be the same as or different from the others, and each is independently selected from among hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 6 -C 10 aryl, C 1 -C 6 alkoxy, C 3 -C 6 alkylsilyl, C 1 -C 6 amino, hydrazino of the formula R a R b NNR c — wherein each of R a , R b and R c may be the same as or different from one another and each is independently selected from among C 1 -C 6 alkyl, and pendant ligands including functional group(s) providing further coordination to the metal center, selected from the group consisting of aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, and groups of the following formulae:

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen and C 1 -C 6 straight chain or branched alkyl, C 1 -C 6 straight chain or branched alkoxy, C 6 -C 10 aryl and NR 5 R 6 ; each of R 5 and R 6 is the same as or different from the other, with each being independently selected from among C 1 -C 6 straight chain or branched alkyl and C 6 -C 10 aryl; n and m are each selected independently from 0 to 4 with the proviso that m and n cannot be 0 at the same time, and x is selected from 1 to 5;

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen, C 1 -C 6 alkyl, and C 6 -C 10 aryl; R 5 is selected from among C 1 -C 6 alkyl, and C 6 -C 10 aryl; and n and m are selected independently from 0 to 4, with the proviso that m and n cannot be 0 at the same time; each L may be the same as or different from the other, each is a unidentate or multidentate Lewis-base ligand, and each is independently selected from the group consisting of phosphines, tertiary phosphines, ethers, polyethers, amines, alkylamines, polyamines, glymes, crown ethers, crown thioethers, cyclic polyamines (cyclenes), thioglymes, C 2 -C 6 alkynes, azoles, imidazoles, C 2 -C 6 alkenes, pyridines, bipyridines, isonitriles, carbenes and hetero-carbenes;

wherein each of R 1 , R 2 , R 3 , R 4 and R 5 may be the same as or different from the others, and each is independently selected from among hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 6 -C 10 aryl, C 1 -C 6 alkoxy, C 3 -C 6 alkylsilyl, C 1 -C 6 amino, hydrazino of the formula R a R b NNR c — wherein each of R a , R b and R c may be the same as or different from one another and each is independently selected from among C 1 -C 6 alkyl, and pendant ligands including functional group(s) providing further coordination to the metal center, selected from the group consisting of aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, and groups of the following formulae:

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen and C 1 -C 6 straight chain or branched alkyl, C 1 -C 6 straight chain or branched alkoxy, C 6 -C 10 aryl and NR 5 R 6 ; each of R 5 and R 6 is the same as or different from the other, with each being independently selected from among C 1 -C 6 straight chain or branched alkyl and C 6 -C 10 aryl; n and m are each selected independently from 0 to 4 with the proviso that m and n cannot be 0 at the same time, and x is selected from 1 to 5;

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen, C 1 -C 6 alkyl, and C 6 -C 10 aryl; R 5 is selected from among C 1 -C 6 alkyl, and C 6 -C 10 aryl; and n and m are selected independently from 0 to 4, with the proviso that m and n cannot be 0 at the same time;

wherein each of R 1 , R 2 , R 3 , R 4 and R 5 may be the same as or different from the others, and each is independently selected from among hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 6 -C 10 aryl, C 1 -C 6 alkoxy, C 3 -C 6 alkylsilyl, C 1 -C 6 amino, hydrazino of the formula R a R b NNR c — wherein each of R a , R b and R c may be the same as or different from one another and each is independently selected from among C 1 -C 6 alkyl, and pendant ligands including functional group(s) providing further coordination to the metal center, selected from the group consisting of aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, and groups of the following formulae:

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen and C 1 -C 6 straight chain or branched alkyl, C 1 -C 6 straight chain or branched alkoxy, C 6 -C 10 aryl and NR 5 R 6 ; each of R 5 and R 6 is the same as or different from the other, with each being independently selected from among C 1 -C 6 straight chain or branched alkyl and C 6 -C 10 aryl; n and m are each selected independently from 0 to 4 with the proviso that m and n cannot be 0 at the same time, and x is selected from 1 to 5;

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen, C 1 -C 6 alkyl, and C 6 -C 10 aryl; R 5 is selected from among C 1 -C 6 alkyl, and C 6 -C 10 aryl; and n and m are selected independently from 0 to 4, with the proviso that m and n cannot be 0 at the same time; L is a unidentate or multidentate Lewis-base ligand selected from the group consisting of phosphines, tertiary phosphines, ethers, polyethers, amines, alkylamines, polyamines, glymes, crown ethers, crown thioethers, cyclic polyamines (cyclenes), thioglymes, C 2 -C 6 alkynes, azoles, imidazoles, C 2 -C 6 alkenes, pyridines, bipyridines, isonitriles, carbenes and hetero-carbenes; and

wherein each of R 1 , R 2 , R 3 , R 4 and R 5 may be the same as or different from the others, and each is independently selected from among hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 6 -C 10 aryl, C 1 -C 6 alkoxy, C 3 -C 6 alkylsilyl, C 1 -C 6 amino, hydrazino of the formula R a R b NNR c — wherein each of R a , R b and R c may be the same as or different from one another and each is independently selected from among C 1 -C 6 alkyl, and pendant ligands including functional group(s) providing further coordination to the metal center, selected from the group consisting of aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl, and acetylalkyl, and groups of the following formulae:

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen and C 1 -C 6 straight chain or branched alkyl, C 1 -C 6 straight chain or branched alkoxy, C 6 -C 10 aryl and NR 5 R 6 ; each of R 5 and R 6 is the same as or different from the other, with each being independently selected from among C 1 -C 6 straight chain or branched alkyl and C 6 -C 10 aryl; n and m are each selected independently from 0 to 4 with the proviso that m and n cannot be 0 at the same time, and x is selected from 1 to 5;

wherein each of R 1 -R 4 is the same as or different from one another, with each being independently selected from among hydrogen, C 1 -C 6 alkyl, and C 6 -C 10 aryl; R 5 is selected from among C 1 -C 6 alkyl, and C 6 -C 10 aryl; and n and m are selected independently from 0 to 4, with the proviso that m and n cannot be 0 at the same time.

Assignments (9)