Titanium Catecholate Catalysis
Hey, I was working on a new idea where I use catecholates for their light absorbing ability, specifically titanium 4+ catecholate, since it has a very
stable pH range.
My idea was to working with it as a catalyst (look up Dr. Gerd Leston and his pioneering work on high selectivity ortho-alkylation of phenols and
polyphenols), for certain reactions. But due to some odd characteristics from previous work I did, it let me to want to try a few options. Dr. Lestons
patents were proven to be useful and seems to be legit, as far as I was able to test in a lab at a fume hood. He has one patent in particular I
noticed (https://patents.google.com/patent/US4431846A/en), but there was another I could not find a link to.
One option was a multilayered plate where the catecholate is used to sensitize Anatase (TiO_x), and they use that to absorb light and transfer an
electron into the band. My hope was to find a way to make a photocatalyst plate.
My other idea was to work on something more like a powder that can be added as a suspension to a reaction flask, and allow for some complex
transformation to occur.
I think one of the main ideas was bound-catalyst systems where the catalyst can be easily retrieved and refreshed, and since the titanium catecholates
seem to not oxidize very fast, I could switch to tert-butyl catechol to avoid that entirely. Since most catecholates have similar ranges of light, we
could fine tune the energy of light to match up whatever reaction we want to occur.
My only experience with the solid-state catalyst is nil, whereas the experience with powdered catalysts is higher, and I have seen evidence
(anecdotally) that this tris-catecholate titanium with elemental zinc can create a stable Ti(3+) ion. I was supposed to use that to rip fluorines and
chlorines off of polymers and monomers, for use in controlling and capping living ring-opening polymerizations. However, I never got to work in that
lab due to personal issues at the time.
But now that I own my own place and have a safe environment to work in again, Id like to begin messing with it. And I was wondering if the community
at large had any input that would help.
To be clear I am not looking to patent. I really just want to learn more and take my college skills and apply them together in a large overarching
project. Even if this amounts to nothing, I want it as a serious learning experience where I can take things at my pace, not University Grad lab pace.
Also, my only experience in transition metal chemistry is titanium. The rest of my experience is within organic reactions and transformations.
Currently, this is my working notes and ideas:
Three ideas so far,
1.) Form Titanates via the method from Ali and Milne (doi:10.1111/j.1151-2916.1993.tb07771.x ) and the subsequent calcination seen in Davies and
Dutremez (doi: 10.1111/j.1151-2916.1990.tb05218.x), followed by reaction with aqueous catechol. Then wash and bake dry. Use as suspension in oily
solvent.
2.) Use regular Titania (TiO_y) and mix into a solution of aqueous catechol. Dry and store under intert atmosphere.
3.) Use the methods seen in Hewage et al. (2022, doi:10.1107/S2056989022002638) as a basis for forming novel heteroleptic mononuclear and dinuclear
complexes, and then use them as catalysts as is, or try to leverage their reactivity to bind them to a polymer or plate. Unfortunately, when I was
taking over the project from Hewage and Mastriano, I ended up spending a lot of time just doing basic characterizations of these complexes, and did
not end up finishing my work on reactivity. I was able to discover some sort of reaction between isopropanol and the tris-catecholate titanium
complex, but was never able to characterize it via NMR. However, all other characteristics deviated from all other complexes, and seems to show a
similar UV-Vis absorbance spectra to that of the Bazhenova et al 2016 (DOI:10.1002/ejic.201600804) paper detailing the bis-DMF bis-catecholate
complex, albeit different. It seems that I know enough to start reaction studies, but I have never planned such a large project.
The attached photo is a uv-vis spectra of titanium catecholate in h2o (DI)
I am the one who boils to dryness, fear me...
H He Li B C(12,14) Na S Cl Mn Fe Cu Zn Ba Ag Sn I U(238)
"I'd rather die on my feet than live on my knees" -Emiliano Zapata
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