Ono pincer ligands and ono pincer ligand comprising metal complexes
Embodiments of the invention are directed to ONO pincer ligands that can be in a trianionic, protonated or protonated equivalent form. The ONO pincer ligand can be combined with a transition metal comprising compound to form an ONO pincer ligand comprising transition metal complex. By choice of the ONO pincer ligand structure, the steric and electronic properties of the transition metal complexes therefrom can be controlled. The ONO pincer ligands comprise a central nitrogen atom that is disubstituted with a pair of three atom comprising bridges where the three atoms are three sp 2 hybridized carbons or the three atoms are a pair of sp 2 hybridized carbons and an sp 3 hybridized carbon or silicon.
1. An ONO trianionic pincer ligand precursor, consisting of a tri-protonated ONO trianionic pincer ligand precursor with OH and NH functionality, wherein each O − from the OH is separated from the N − from the NH by three bridging carbons, wherein the O − s and the N − and the bridging carbons are capable of assuming a coplanar substructure:
where X is C, and wherein the tri-protonated ONO trianionic pincer ligand precursor with OH and NH functionality has the structure:
wherein R is independently C 2 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 1 -C 30 alkoxy, C 2 -C 30 alkenyloxy, C 2 -C 30 alkynyloxy, 2 -C 30 alkylester, C 3 -C 30 alkenylester, C 3 -C 30 alkynylester, or perfluorinated, partially fluorinated variations thereof.
2. The ONO trianionic pincer ligand precursor of claim 1 , consisting of a tri-protonated ONO trianionic pincer ligand precursor with OH and NH functionality, wherein each O − from the OH is separated from the N − from the NH by three bridging carbons, wherein the O − s and the N − and the bridging carbons are capable of assuming a coplanar substructure:
where X is C, and wherein the tri-protonated ONO trianionic pincer ligand precursor with OH and NH functionality has the structure:
wherein R is independently C 2 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 1 -C 30 alkoxy, C 2 -C 30 alkenyloxy, C 2 -C 30 alkynyloxy, 2 -C 30 alkylester, C 3 -C 30 alkenylester, C 3 -C 30 alkynylester, or perfluorinated, partially fluorinated variations thereof.
3. The ONO trianionic pincer ligand precursor of claim 1 , consisting of a tri-protonated ONO trianionic pincer ligand precursor with OH and NH functionality, wherein each O − from the OH is separated from the N − from the NH by three bridging carbons, wherein the O − s and the N − and the bridging carbons are capable of assuming a coplanar substructure:
where X is C, and wherein the tri-protonated ONO trianionic pincer ligand precursor with OH and NH functionality has the structure:
wherein R is independently C 2 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 1 -C 30 alkoxy, C 2 -C 30 alkenyloxy, C 2 -C 30 alkynyloxy, 2 -C 30 alkylester, C 3 -C 30 alkenylester, C 3 -C 30 alkynylester, or perfluorinated, partially fluorinated variations thereof.
4. The ONO trianionic pincer ligand precursor of claim 2 , wherein the structure is:
5. The ONO trianionic pincer ligand precursor of claim 3 , wherein the structure is:
6. A trianionic ONO pincer ligand comprising transition metal complex comprising:
at least one ONO trianionic pincer ligand derived from the ONO trianionic pincer ligand precursor of claim 1 ; and
a transition metal from group III through group X of the periodic table.
7. The trianionic ONO pincer ligand comprising transition metal complex of claim 6 , wherein the transition metal is an early transition metal complex from group III through group VI.
8. The trianionic ONO pincer ligand comprising transition metal complex of claim 6 , wherein the structure is:
9. The trianionic ONO pincer ligand comprising transition metal complex of claim 6 , wherein the structure is:
10. The trianionic ONO pincer ligand comprising transition metal complex of claim 6 , wherein the structure is:
11. A method of preparing an ONO pincer ligand precursor according to claim 1 , comprising condensing a nucleophilic oxygen or nucleophilic nitrogen comprising compound with an electrophilic carbon comprising compound further comprising the bridge structure of the resulting ONO pincer ligand.
12. A method of preparing an ONO pincer ligand comprising transition metal complex of claim 6 , comprising combining a precursor metal compound comprising a metal alkoxide or metal amide with an ONO pincer ligand precursor of the structure:
wherein R is independently C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 2 -C 30 alkynyl, C 6 -C 2 -C 30 alkenyloxy, C 2 -C 30 alkynyloxy, C 2 -C 30 alkylester, C 3 -C 30 alkenylester, C 3 -C 30 alkynylester, or perfluorinated, partially fluorinated, and/or otherwise substituted variations thereof; wherein proton and ligand exchange between the anionic ONO pincer ligand precursor and the metal alkoxide or metal amide.
13. The method of preparing an ONO pincer ligand comprising transition metal complex of claim 12 , wherein the precursor metal compound further comprises a metal alkylidyne, further comprising adding the OH or NH of the ONO pincer ligand precursor across the metal alkylidyne to form the anionic ONO pincer ligand comprising metal complex.