STERICALLY MODIFIED SCHIFF BASE LIGANDS FOR ENHANCED CATALYTIC CARBONYLATION ACTIVITY

1 . A composition, comprising:

a) a metal carbonyl anion; and

b) a cation ionically bonded to the metal carbonyl anion, comprising:

i) a ligand including two residues of 3,5-substituted salicylaldehydes connected by a hydrocarbyl-diimine bridge that includes a nitrogen atom contacted with a carbon of an aldehyde residue at each of the two residues of the 3,5-substituted salicylaldehydes, wherein each of the residues of the 3,5-substituted salicylaldehydes are independently substituted at 3 position by a hydrocarbyl group that is a branched alkyl-aryl group, and wherein each of the residues of the 3,5-substituted salicylaldehydes are independently substituted at a 5 position by a hydrogen, methyl, a —C 2 -C 12 , alkyl group, an aryl group, a t-butyl alkyl group, a halogen, an amine, —CF 5 , hydrocarbyl oxy group, or —NO 2 ;

ii) a metal coordinated with the ligand at each hydroxyl residue the two residues of the 3,5-substituted salicylaldehydes at a 2 position and at each of the nitrogen atoms of the hydrocarbyl-diimine bridge; and

iii) two polar ligands coordinated with the metal.

2 . The composition of claim 1 , wherein the composition, comprises:

wherein M is a metal;

wherein PL is a polar ligand;

wherein each R 1 is independently a hydrocarbyl group comprising a branched alky-aryl group;

wherein each R 2 is independently selected from one or more of a hydrogen atom, a methyl group, a C 2-16 alkyl group, an aryl group, an alkyl-aryl group, a halogen, an amine, a trifluoromethyl group, a nitro group, a hydrocarbyl oxy group, or any combination thereof;

wherein at least one of R 1 or R 2 is selected from an alkyl group, an aryl group, or an alkyl-aryl group that contains at least 5 carbons; and

wherein each R 3 is independently selected from hydrogen, methyl, a C 2-10 alkyl group, a combination thereof, or in combination form a six membered ring that is optionally a substituted aromatic ring.

3 . The composition of claim 2 , wherein each R 1 is independently selected from one or more of a 1,1 ethylphenyl propane, 2,2 methylphenyl ethane, 1,1-diphenylethyl, or any combination thereof.

4 . The composition of claim 2 , wherein each R 2 is independently selected from one or more of a methyl group, a C 2-16 alkyl group, an aryl group, an alkyl-aryl group, or any combination thereof.

5 . The composition of claim 1 , wherein each of the 3,5-substituted phenyls are independently substituted at the 3 position by one or more of 1,1 ethylphenyl propane, 2,2 methylphenyl ethane, 1,1-diphenylethyl, or any combination thereof.

6 . The composition of claim 1 , wherein the ligand, comprises:

wherein each R 1 is independently a hydrocarbyl group comprising a branched alkyl-aryl group;

wherein each R 2 is independently selected from one or more of a hydrogen atom, a methyl group, a C 2-16 alkyl group, an aryl group, an alkyl-aryl group, a halogen, an amine, a trifluoromethyl group, a nitro group, a hydrocarbyl oxy group, or any combination thereof;

wherein at least one of R 1 or R 2 is selected from an alkyl group, an aryl group, or an alkyl-aryl group that contains at least 5 carbons; and

wherein each R 3 is independently selected from hydrogen, methyl, a C 2-10 alkyl group, a combination thereof, or in combination form a six membered ring that is optionally a substituted aromatic ring.

7 . (canceled)

8 . (canceled)

9 . The composition claim 2 , wherein the metal carbonyl anion comprises (Co(CO) 4 ).

10 . (canceled)

11 . (canceled)

12 . (canceled)

13 . The composition of claim 2 , wherein the metal includes one or more of Al or Cr.

14 . (canceled)

15 . (canceled)

16 . (canceled)

17 . (canceled)

18 . A method, comprising:

a) contacting a ligand with a metalating agent to form a metal centered compound, wherein the ligand includes the residues of two 3, 5-substituted salicylaldehydes connected by an hydrocarbyl-diimine bridge at the aldehyde residue of the two residues of the 3,5-substituted salicylaldehydes, wherein each substitution at a 3 position comprises a hydrocarbyl group comprising an alkyl-aryl group and wherein each substitution of the 3,5-substituted salicylaldehydes at a 5 position comprises hydrogen, methyl, a —C 2 -C 12 , alkyl group, an aryl group, a t-butyl alkyl group, a halogen, an amine, —CF 5 , hydrocarbyl oxy group, or —NO 2 ; and

b) contacting the metal centered compound with a metal carbonyl and a polar ligand to form a composition.

19 . The method of claim 18 , wherein the method comprises:

a) contacting a compound according to the following formula:

with a metalating agent to form one of the compounds according to the following formula:

b) contacting the formed compounds with a metal carbonyl and a polar ligand under conditions so that one of the following compositions are formed:

wherein M is a metal;

wherein each PL is the polar ligand;

wherein each R 1 is independently a hydrocarbyl group comprising a branched alkyl-aryl group;

wherein each R 2 is independently selected from one or more of a hydrogen atom, a methyl group, a C 2-16 alkyl group, an aryl group, an alkyl-aryl group, a halogen, an amine, a trifluoromethyl group, a nitro group, a hydrocarbyl oxy group, or any combination thereof;

wherein at least one of R 1 or R 2 is selected from an alkyl group, an aryl group, or an alkyl-aryl group that contains at least 5 carbons; and

wherein each R 3 is independently selected from hydrogen, methyl, a C 2-10 alkyl group, a combination thereof, or in combination form a six membered ring that is optionally a substituted aromatic ring.

20 . The method of claim 19 , wherein each R 1 is independently selected from one or more of 1,1 ethylphenyl propane, 2,2 methylphenyl ethane, 1,1-diphenylethyl, or any combination thereof.

21 . The method of claim 19 , wherein each R 2 is independently selected from one or more of methyl group, a C 1-16 alkyl group, an aryl group, an alkyl-aryl group, or any combination thereof.

22 . The method of claim 19 , wherein the polar ligand includes one or more of tetrahydrofuran, diethyl ether, dioxane, or any combination thereof.

23 . The method of claim 19 , wherein the R 2 is independently selected from one or more of hydrogen, —CH 3 , a —C 2 -C 12 alkyl group, or an aryl group.

24 . The method of any one of claim 19 , wherein the metal includes one or more of Al or Cr.

25 . The method of claim 19 , wherein the metalating agent includes one or more of (Et) 2AlCl, (Et) 3Al, CrCl 2 , or any combination thereof, and/or wherein the metal carbonyl includes one or more of NaCo(CO) 4 , Co 2 (CO) 8, HCo(CO) 4 , or a combination thereof.

26 . (canceled)

27 . A method, comprising contacting an epoxide and carbon monoxide in the presence of a carbonylation catalyst to form beta propiolactone,

wherein the carbonylation catalyst comprises:

c) a metal carbonyl anion; and

d) a cation ionically bonded to the metal carbonyl anion, comprising:

i) a ligand including two residues of 3,5-substituted salicylaldehydes connected by a hydrocarbyl-diimine bridge that includes a nitrogen atom contacted with a carbon of an aldehyde residue at each of the two residues of the 3,5-substituted salicylaldehydes, each of the residues of the 3,5-substituted salicylaldehydes independently substituted at one or both of a 3 position and a 5 position by a hydrocarbyl group comprising an alkyl-aryl group containing at least 5 carbons;

ii) a metal coordinated with the ligand at each hydroxyl residue of a 2 position of the two residues of the 3,5-substituted salicylaldehydes and at each of the nitrogen atoms of the hydrocarbyl-diimine bridge; and

iii) two polar ligands coordinated with the metal.

28 . The method of claim 27 , wherein the carbonylation catalyst has a structure according to the following formula:

wherein M is a metal;

wherein PL is a polar ligand;

wherein each R 1 is independently hydrocarbyl group comprising a branched alkyl-aryl group;

wherein each R 2 is independently selected from one or more of a hydrogen atom, a methyl group, a C 2-16 alkyl group, an aryl group, an alkyl-aryl group, a halogen, an amine, a trifluoromethyl group, a nitro group, a hydrocarbyl oxy group, or any combination thereof;

wherein at least one of R 1 or R 2 is selected from an alkyl group, an aryl group, or an alkyl-aryl group that contains at least 5 carbons; and

wherein each R 3 is independently selected from hydrogen, methyl, a C 2-10 alkyl group, a combination thereof, or in combination form a six membered ring that is optionally a substituted aromatic ring.

29 . (canceled)

30 . The method of claim 27 , wherein the metal is Al or Cr.

31 . The method of claim 27 , wherein R 1 is independently selected from one or more of 1,1 ethylphenyl propane, 2,2 methylphenyl ethane, 1,1-diphenylethyl, or any combination thereof.