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US 10,300,469 B1Granted
Metal-ligand cooperative catalysis through N-H arm deprotonation/pyridine dearomatiztion for efficient hydrogen generation from formic acid
AssigneeKing Abdullah University of Science and Technology
InventorsKuo-Wei Huang, Chengling Pan, Yupeng Pan
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Abstract
The invention describes phospho-amino pincer-type ligands, metal complexes thereof, and catalytic methods comprising such metal complexes.
Claims21
A method to produce hydrogen from formic acid comprising the step of contacting formic acid with a complex comprising a ligand and a metal or metal ion, wherein the ligand is a compound according to formula (I), or a deprotonated version thereof, and the ligand is associated with the metal or metal ion, wherein formula (I) comprises:
- wherein R1 and R2, are each independently alkyl(C≤12), aryl(C≤12), aralkyl(C≤12), or a substituted version of any of these groups;
- R3, and R4, if present, are each independently alkyl(C≤12), aryl(C≤12), aralkyl(C≤12), or a substituted version of any of these groups;
- R5 is a hydrogen atom or an alkyl(C≤12), aryl(C≤12), aralkyl(C≤12), amino, hydroxyl, alkoxyl or a substituted version of any of these groups;
- each Z, independently, is CR6, N or P;
- R6 is a hydrogen atom or an alkyl(C≤12), aryl(C≤12), aralkyl(C≤12), amino, hydroxyl, alkoxyl or a substituted version of any of these groups;
- T is a N, NR7, CR8, or CR9R10;
- R7, R8, R9 and R10 are each independently a hydrogen, alkyl(C≤12), aryl(C≤12), aralkyl(C≤12), or a substituted version of any of these groups;
- Q is P or N;
- optionally, wherein T and Q, together, form a 5 or 6 membered heterocyclic ring;
- wherein the heterocyclic ring can optionally be substituted with one or more heteroatoms and or one or more sites of the heterocyclic ring are substituted with one or more alkyl(C≤12), aryl(C≤12), aralkyl(C≤12), or a substituted version of any of these groups, and optionally wherein the heterocyclic ring can have a fused ring attached thereto, provided when T and Q form a 5 or 6 membered heterocyclic ring, R3 and R4 are not present;
- and
- designates a single bond or a double bond.
9 more elements
A method to produce hydrogen from formic acid comprising the step of contacting formic acid with a compound of formula (II):
- wherein R1 and R2, are each independently alkyl(C≤12), aryl(C≤12), aralkyl(C≤12), or a substituted version of any of these groups;
- R3, and R4, if present, are each independently alkyl(C≤12), aryl(C≤12), aralkyl(C≤12), or a substituted version of any of these groups;
- R5 is a hydrogen atom or an alkyl(C≤12), aryl(C≤12), aralkyl(C≤12), or a substituted version of any of these groups;
- each Z, independently, is CR6, N or P;
- R6 is a hydrogen atom or an alkyl(C≤12), aryl(C≤12), aralkyl(C≤12), amino , hydroxyl, alkoxyl or a substituted version of any of these groups;
- M is a metal or metal ion that is a group 8 metal or metal ion;
- L is a neutral or an anionic ligand;
- n is 0, 1 or 2;
- X is a halide or a hydrogen atom;
- T is a N, NR7, CR8, or CR9R10;
- R7, R8, R9 and R10 are each independently a hydrogen, alkyl(C≤12), aryl(C≤12), aralkyl(C≤12), or a substituted version of any of these groups;
- Q is P or N;
- optionally, wherein T and Q, together, from a 5 or 6 membered heterocyclic ring;
- wherein the heterocyclic ring can optionally be substituted with one or more heteroatoms and or one or more sites of the heterocyclic ring are substituted with one alkyl(C≤12), aryl(C≤12), aralkyl(C≤12), or a substituted version of any of these groups, and optionally wherein the heterocyclic ring can have a fused ring attached thereto, provided when T and Q form a 5 or 6 membered heterocyclic ring, R3 and R4 are not present;
- and
- designates a single bond or a double bond.
13 more elements
A method to produce hydrogen from formic acid comprising the step of contacting formic acid with a compound of formula (III):
- wherein R1 and R2, are each independently alkyl(C≤12), aryl(C≤12), aralkyl(C≤12), or a substituted version of any of these groups;
- R3, and R4, if present, are each independently alkyl(C≤12), aryl(C≤12), aralkyl(C≤12), or a substituted version of any of these groups;
- R5 is a hydrogen atom or an alkyl(C≤12), aryl(C≤12), aralkyl(C≤12), or a substituted version of any of these groups;
- each Z, independently, is C6, N or P;
- R6 is a hydrogen atom or an alkyl(C≤12), aryl(C≤12), aralkyl(C≤12), amino, hydroxyl, alkoxyl or a substituted version of any of these groups;
- T is a N, NR7, CR8, or CR9R10;
- R7, R8, R9 and R10 are each independently a hydrogen, alkyl(C≤12), aryl(C≤12), aralkyl(C≤12), or a substituted version of any of these groups;
- Q is P or N;
- M is a metal or metal ion that is a group 8 metal or metal ion;
- L is a neutral or an anionic ligand;
- n is 0, 1 or 2;
- X is a halide or a hydrogen atom;
- and
- optionally, wherein T and Q, together, form a 5 or 6 membered heterocyclic ring;
- wherein the heterocyclic ring can optionally be substituted with one or more heteroatoms and or one or more sites of the heterocyclic ring are substituted with one alkyl(C≤12), aryl(C≤12), aralkyl(C≤12), or a substituted version of any of these groups, and optionally wherein the heterocyclic ring can have a fused ring attached thereto, provided when T and Q form a 5 or 6 membered heterocyclic ring, R3 and R4 are not present;
- and
- designates a single bond or a double bond.
14 more elements
Dependencies are inferred from the claim text.