IP Library › Granted Patent US 11,008,353

Granted Patent B2

US 11,008,353 · App. 16/035,348 · Granted May 18, 2021

Metal complexes for depositing films and method of making and using the same

Inventors: Gregory S. Girolami (Champaign, IL); Sumeng Liu (Nanjin, CN)

Assignee: The Board of Trustees of the University of Illinois

C07F15/0086 C07F1/02 C07F15/0033 C07F15/0073 C23C16/18 C23C16/45553

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Quick Facts

Patent No.: US 11,008,353
App. No.: 16/035,348
Granted: May 18, 2021
Kind: B2

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Abstract

Provided herein are metal-ligand complexes, and associated methods, characterized by formula ML x D y ; wherein: M is a metal; x is equal to the oxidation state of M; each D is independently a neutral coordinating ligand; y is zero or an integer selected from the range of 1 to 4; and each L is independently a mono-anionic ligand. L may be a η 1 ,η 2 -β,β-disubstituted-ω-alkenyl ligand.

Claims (145)

1. A metal-ligand complex, said metal-ligand complex being characterized by formula (FX1):

ML x D y (FX1),

wherein:

M is a metal selected from the group consisting of Be, Mg, Ca, Sr, Ba, Al, Sc, Ga, Sn, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, a lanthanide metal, and an actinide metal;

x is equal to the oxidation state of M;

each D is independently a neutral coordinating ligand;

y is zero or an integer selected from the range of 1 to 4; and

each L is a mono-anionic ligand independently characterized by the formula FX2:

and wherein:

each R 1 and R 2 is independently selected from the group consisting of a halide and a substituted or unsubstituted C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 heterocycloalkyl, C 1 -C 6 haloalkyl, C 6 -C 10 alkylaryl, C 1 -C 6 alkoxy, C 6 -C 10 aryl, C 6 -C 10 heteroaryl, silyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 1 -C 6 hydroxyl, C 3 -C 10 arylene, C 3 -C 10 heteroarylene, C 2 -C 10 alkenylene, C 3 -C 10 cycloalkenylene, C 2 -C 10 alkynylene, or any combination thereof;

each of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 is independently selected from the group consisting of a hydrogen, a halide, and a substituted or unsubstituted C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 heterocycloalkyl, C 1 -C 6 haloalkyl, C 6 -C 10 alkylaryl, C 1 -C 6 alkoxy, C 6 -C 10 aryl, C 6 -C 10 heteroaryl, silyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 1 -C 6 hydroxyl, C 3 -C 10 arylene, C 3 -C 10 heteroarylene, C 2 -C 10 alkenylene, C 3 -C 10 cycloalkenylene, C 2 -C 10 alkynylene, or any combination thereof; and

E is C or Si;

with a proviso that at least one of R 1 and R 2 is not a fluoride or a trifluoromethyl; and

wherein M is associated with each L via both a metal-carbon sigma bond and a metal-olefin pi bond.

2. The metal-ligand complex of claim 1 , wherein at least one of R 1 and R 2 is not a fluoride or a C 1 -C 6 fluoroalkyl.

3. The metal-ligand complex of claim 1 , wherein each of both R 1 and R 2 is not a fluoride or a trifluoromethyl.

4. The metal-ligand complex of claim 1 , wherein each of both R 1 and R 2 is not a fluoride or a C 1 -C 6 fluoroalkyl.

5. The metal-ligand complex of claim 1 , wherein M is selected from the group consisting of Be, Mg, Ca, Sr, Ba, Al, Sc, Ga, Sn, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, and a lanthanide metal.

6. The metal-ligand complex of claim 1 , wherein a coordination number of M is 4 or 6.

7. The metal-ligand complex of claim 1 , wherein L is a η 1 , η 2 -β, β-disubstituted-ω-alkenyl ligand.

8. The metal-ligand complex of claim 1 , wherein when x is greater than 1, each L is identical.

9. The metal-ligand complex of claim 1 , wherein when x is greater than 1, each L is different from each other L.

10. The metal-ligand complex of claim 1 wherein the total number of carbon atoms in each L excluding R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 is independently 4 or 5.

11. The metal-ligand complex of claim 1 , wherein when x is greater than 1, the metal-carbon sigma bonds in said metal-ligand complex are cis with respect to each other.

12. The metal-ligand complex of claim 1 , wherein L is a bidentate ligand.

13. The metal-ligand complex of claim 1 , wherein each D independently comprises an ether group (R 10 2 O), an amine group (R 10 3 N), a nitrile group (R 10 CN), an isonitrile group (R 10 NC), a phosphine group (R 10 3 P), a phosphite group ((R 10 O) 3 P), an arsine group (R 10 3 As), a stibene group (R 10 3 Sb), a sulfide group (CS), a linear, branched, or cyclic monoalkene, a linear, branched, or cyclic diene, a linear, branched, or cyclic triene, bicyclic alkene, bicyclic dienes bicyclic triene, tricyclic diene, tricyclic triene, alkyne, and any combination thereof; wherein each R 10 is independently selected from the group consisting of a substituted or unsubstituted C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 heterocycloalkyl, C 1 -C 6 haloalkyl, C 6 -C 10 alkylaryl, C 1 -C 6 alkoxy, C 6 -C 10 aryl, C 6 -C 10 heteroaryl, silyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 1 -C 6 hydroxyl, C 3 -C 10 arylene, C 3 -C 10 heteroarylene, C 2 -C 10 alkenylene, C 3 -C 10 cycloalkenylene, C 2 -C 10 alkynylene, and any combination thereof.

14. The metal-ligand complex of claim 1 , wherein each D is independently selected from the group consisting of 1,5-cyclooctadiene, bicyclo[2.2.1]hepta-2,5-diene, 1,5-hexadiene, ethylene, dibenzo[a,e]cyclooctene, N,N,N′,N′-tetramethylethylenediamine, and acetonitrile.

15. The metal-ligand complex of claim 1 , wherein y is 0.

16. The metal-ligand complex of claim 1 being selected from the group consisting of cis-bis(η 1 , η 2 -2,2-dimethylbut-3-en-1-yl)platinum, cis-bis(η 1 , η 2 -2,2-dimethylpent-4-en-1-yl)platinum, cis-bis(η 1 , η 2 -2,2-dimethylhex-5-en-1-yl)platinum, [(1,2,5,6-η)-1,5-cyclooctadiene](η 1 , η 2 -2,2-dimethylpent-4-en-1-yl)iridium, [(1,2,5,6-η)-1,5-cyclooctadiene](η 1 , η 2 -2,2-dimethylpent-4-en-1-yl)rhodium, and [(2,3,5,6-η)-bicyclo[2.2.1]hepta-2,5-diene](η 1 , η 2 -2,2-dimethyl-pent-4-en-1-yl)rhodium.

17. The metal-ligand complex of claim 1 being characterized by the formula FX3:

18. The metal-ligand complex of claim 1 being characterized by the formula FX4:

19. The metal-ligand complex of claim 1 , wherein less than 10 mass % of said metal-ligand complex decomposes after two weeks when stored under at least 1 atm of one or more inert gases at room temperature.

20. The metal-ligand complex of claim 1 having a thermolysis onset temperature selected from the range of 50° C. to 300° C.; wherein said thermolysis onset temperature is measured using thermogravimetric analysis with a temperature increase rate of 10° C./min and under approximately 1 atm of N 2 .

21. The metal-ligand complex of claim 1 , wherein said metal-ligand complex does not decompose via beta-hydrogen elimination at NTP.

22. The metal-ligand complex of claim 1 being a hydrosilylation catalyst or a hydrosilylation catalyst precursor.

23. The metal-ligand complex of claim 1 being a vapor-to-solid precursor.

24. The metal-ligand complex of claim 1 , wherein M has an oxidation number of at least +2.

25. A vapor-to-solid precursor comprising a metal-ligand complex, said metal-ligand complex being characterized by formula (FX1):

ML x D y (FX1),

wherein:

x is equal to the oxidation state of M;

each D is independently a neutral coordinating ligand;

y is zero or an integer selected from the range of 1 to 4; and

each L is a mono-anionic ligand independently characterized by the formula FX2:

and wherein:

E is C or Si; and

wherein M is associated with each L via both a metal-carbon sigma bond and a metal-olefin pi bond.

26. The vapor-to-solid precursor of claim 25 , wherein M has an oxidation number of at least +2.

27. A method for depositing a solid material on a substrate, said method comprising steps of:

exposing a receiving surface of said substrate to a vapor of a vapor-to-solid precursor;

wherein said vapor-to-solid precursor comprises a metal-ligand complex;

wherein said metal-ligand complex is characterized by formula (FX1):

ML x D y (FX1),

wherein:

x is equal to the oxidation state of M;

each D is independently a neutral coordinating ligand;

y is zero or an integer selected from the range of 1 to 4; and

each L is a mono-anionic ligand independently characterized by the formula FX2:

and wherein:

E is C or Si; and

wherein M is associated with each L via both a metal-carbon sigma bond and a metal-olefin pi bond; and

decomposing said metal-ligand complex at said receiving surface of said substrate;

thereby forming said solid material, wherein said solid material comprises M.

28. A method for forming a metal-ligand complex, comprising:

combining a starting compound and a Grignard reagent or an organolithium reagent;

wherein said metal-ligand complex is characterized by formula (FX1):

ML x D y (FX1),

wherein:

x is equal to the oxidation state of M;

each D is independently a neutral coordinating ligand;

y is zero or an integer selected from the range of 1 to 4; and

each L is a mono-anionic ligand independently characterized by the formula FX2:

and wherein:

E is C or Si; and

wherein M is associated with each L via both a metal-carbon sigma bond and a metal-olefin pi bond.

29. A method for catalytic hydrosilylation of a starting compound, said method comprising steps of:

hydrosilylating said starting compound in the presence of a hydrosilylation catalyst;

wherein said hydrosilylation catalyst comprises a metal-ligand complex or wherein said hydrosilylation catalyst is formed by activation of a hydrosilylation precatalyst that comprises said metal-ligand complex; and

wherein said metal-ligand complex is characterized by formula (FX1):

ML x D y (FX1),

where:

x is equal to the oxidation state of M;

each D is independently a neutral coordinating ligand;

y is zero or an integer selected from the range of 1 to 4; and

each L is a mono-anionic ligand independently characterized by the formula FX2:

where:

E is C or Si; and

wherein M is associated with each L via both a metal-carbon sigma bond and a metal-olefin pi bond.

30. A metal-ligand complex, said metal-ligand complex being characterized by formula (FX1):

ML x D y (FX1),

wherein:

x is equal to the oxidation state of M;

each D is independently a neutral coordinating ligand;

y is zero or an integer selected from the range of 1 to 4; and

each L is a mono-anionic ligand independently characterized by the formula FX2:

and wherein:

each of R 3 , R 4 , R 5 , R 6 , R 7 , Fe, and R 9 is independently selected from the group consisting of a hydrogen, a halide, and a substituted or unsubstituted C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 heterocycloalkyl, C 1 -C 6 haloalkyl, C 6 -C 10 alkylaryl, C 1 -C 6 alkoxy, C 6 -C 10 aryl, C 6 -C 10 heteroaryl, silyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 1 -C 6 hydroxyl, C 3 -C 10 arylene, C 3 -C 10 heteroarylene, C 2 -C 10 alkenylene, C 3 -C 10 cycloalkenylene, C 2 -C 10 alkynylene, or any combination thereof; and

E is C or Si;

with a proviso that at least one of R 1 and R 2 is not a fluoride or a trifluoromethyl; and

wherein when x is greater than 1, each L is different from each other L.

31. A metal-ligand complex, said metal-ligand complex being characterized by formula (FX1):

ML x D y (FX1),

wherein:

x is equal to the oxidation state of M;

each D is independently a neutral coordinating ligand;

y is an integer selected from the range of 1 to 4; and

each L is a mono-anionic ligand independently characterized by the formula FX2:

and wherein:

E is C or Si;

with a proviso that at least one of R 1 and R 2 is not a fluoride or a trifluoromethyl;

wherein each D independently comprises an ether group (R 10 2 O), an amine group (R 10 3 N), a nitrile group (R 10 CN), an isonitrile group (R 10 NC), a phosphine group (R 10 3 P), a phosphite group ((R 10 O) 3 P), an arsine group (R 10 3 As), a stibene group (R 10 3 Sb), a sulfide group (R 10 2 S), a linear, branched, or cyclic monoalkene, a linear, branched, or cyclic diene, a linear, branched, or cyclic triene, bicyclic alkene, bicyclic dienes bicyclic triene, tricyclic diene, tricyclic triene, alkyne, and any combination thereof; wherein each R 10 is independently selected from the group consisting of a substituted or unsubstituted C 1 -C 6 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 heterocycloalkyl, C 1 -C 6 haloalkyl, C 6 -C 10 alkylaryl, C 1 -C 6 alkoxy, C 6 -C 10 aryl, C 6 -C 10 heteroaryl, silyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 1 -C 6 hydroxyl, C 3 -C 10 arylene, C 3 -C 10 heteroarylene, C 2 -C 10 alkenylene, C 3 -C 10 cycloalkenylene, C 2 -C 10 alkynylene, and any combination thereof; and

wherein M is associated with each L via both a metal-carbon sigma bond and a metal-olefin pi bond.

32. A metal-ligand complex, said metal-ligand complex being characterized by formula (FX1):

ML x D y (FX1),

wherein:

x is equal to the oxidation state of M;

each D is independently a neutral coordinating ligand;

y is an integer selected from the range of 1 to 4; and

each L is a mono-anionic ligand independently characterized by the formula FX2:

and wherein:

E is C or Si;

with a proviso that at least one of R 1 and R 2 is not a fluoride or a trifluoromethyl;

wherein each D is independently selected from the group consisting of 1,5-cyclooctadiene, bicyclo[2.2.1]hepta-2,5-diene, 1,5-hexadiene, ethylene, dibenzo[a,e]cyclooctene, N, N, N′,N′-tetramethylethylenediamine, and acetonitrile; and

wherein M is associated with each L via both a metal-carbon sigma bond and a metal-olefin pi bond.

33. A metal-ligand complex, wherein the metal-ligand complex is characterized by the formula FX4:

Assignments (2)

ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 12, 2019

From: GIROLAMI, GREGORY S.; LIU, SUMENG

To: THE BOARD OF TRUSTEES OF THE UNIVERSITY OF ILLINOIS

Reel/Frame 048867/0114 →

CONFIRMATORY LICENSE Recorded Aug 1, 2018

From: UNIVERSITY OF ILLINOIS, URBANA-CHAMPAIGN

To: NATIONAL SCIENCE FOUNDATION

Reel/Frame 046683/0065 →

Continuity (2)

Provisional Application 62532452 · Jul 14, 2017

Related Publication 20190077819A1 · Mar 14, 2019