ONO PINCER LIGANDS AND ONO PINCER LIGAND COMPRISING METAL COMPLEXES

• US 20140073800A1
• Filed: 11/12/2013
• Published: 03/13/2014
• Est. Priority Date: 05/11/2011
• Status: Active Grant

• Current Assignee: University of Florida Research Foundation, Incorporated (State University System of Florida)
• Original Assignee: University of Florida Research Foundation, Incorporated (State University System of Florida)
• Inventors: VEIGE, ADAM STEVEN, O'REILLY, MATTHEW, JAN, MUHAMMAD TARIQ
• Granted Patent: US 9,464,104 B2
• Time in Patent Office: Days
• US Class Current: 548/403
• CPC Class Codes: C07C 213/02 by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
• CPC Class Codes: C07C 215/50 with amino groups and the six-membered aromatic ring, or the condensed ring system containing that ring, bound to the same carbon atom of the carbon chain
• CPC Class Codes: C07C 215/68 having amino groups bound to carbon atoms of six-membered aromatic rings and hydroxy groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
• CPC Class Codes: C07C 215/82 having the nitrogen atom of at least one of the amino groups further bound to a carbon atom of another six-membered aromatic ring
• CPC Class Codes: C07F 11/00 Compounds containing elements of Groups 6 or 16 of the Periodic Table
• CPC Class Codes: C07F 11/005 compounds without a metal-carbon linkage
• CPC Class Codes: C07F 9/5456 Arylalkanephosphonium compounds

Abstract

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 sp² hybridized carbons or the three atoms are a pair of sp² hybridized carbons and an sp³ hybridized carbon or silicon.

Claims

1. An ONO trianionic pincer ligand precursor, comprising a tri-protonated ONO trianionic pincer ligand precursor with OH and NH functionality or a ONO trianionic pincer ligand precursor having functional equivalents to OH and NH, wherein each O⁻

from the OH or the functional equivalent thereof are separated from the N⁻

from the NH or the functional equivalent thereof by three bridging carbons or two bridging carbons and a silicon, wherein the O⁻

s and the N⁻

and the bridging carbons or the bridging carbons and silicons are capable of assuming a coplanar substructure;

2. The ONO trianionic pincer ligand precursor of claim 1, wherein the structure is:

3. The ONO trianionic pincer ligand precursor of claim 1, wherein the structure is:

4. The ONO trianionic pincer ligand precursor of claim 1, wherein the structure is:

5. 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.

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. The trianionic ONO pincer ligand comprising transition metal complex of claim 6, wherein the structure is:

12. The trianionic ONO pincer ligand comprising transition metal complex of claim 6, wherein the structure is:

13. The trianionic ONO pincer ligand comprising transition metal complex of claim 6, wherein the structure is:

14. The trianionic ONO pincer ligand comprising transition metal complex of claim 6, wherein the structure is:

15. The trianionic ONO pincer ligand comprising transition metal complex of claim 6, wherein the structure is:

16. The trianionic ONO pincer ligand comprising transition metal complex of claim 6, wherein the structure is:

17. 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:

18. The method of preparing an ONO pincer ligand comprising transition metal complex of claim 17, 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.