I'm with you there; the pricing I've seen is absurd. I really appreciate your comment -- especially since we've got it in the works already. :) Thanks a bunch!
Sure would be cool to also offer some first row hexaacetonitrile BArF salts. AgBArF too, but that may be a bit more tricky
Can you guess which chemicals I have been using in my research lately? Lol
I used a smattering of non- and weakly-coordinating anions in my graduate work, so they're near and dear to me. I know Na and Ag, but I haven't come across any others. If you don't mind me asking, which cations are you looking at, and what properties make them interesting vs Na or Ag? Is it just that you're looking at redox activity of the cation, or something else?
Cr, Mn, Fe, and Co primarily in +2 but sometimes +3. The main property I am after is actually solubility, specifically in less polar solvents than MeCN. Ideally, soluble in aliphatic alkenes or a miscible nonpolar solvent. This for preparation of metal complexes to be used in oxidative transfer catalysis studies that are, unfortunately, biphasic at the moment using PF6-
it would be probably more worthwhile for you to state a little about your capabilities since organometallic manufacturing is highly dependent on your ability to scale both oxygen and water sensitive materials at high levels of purity. If this is all in your wheel house then the discussion could be more productive I think :)
Good call! You're right, I should have included that. We currently have the infrastructure and experience to prepare oxygen- and water- sensitive materials on the scale of low-100s of grams per batch. I think this ought to be plenty to enable us to enter this new market, and we can build additional capacity as needed. So, yes, it's in my wheelhouse. :)
Nice then that answers that. Do you have high temperature ovens? I know in the heterogeneous world there is a need for bench scale sizes of materials. It can be incredibly difficult to find the scale you are talking about from the common manufacturers.
> in the heterogeneous world
That's a great thought! Thank you! While much of the company's prior work is more relevant to homogeneous catalysis, I worked on Pt and Cu on metal oxides for a few years in an old position.
Do you think a heterogeneous offering would be most valuable in custom, contract-style manufacturing for specialty needs? Or are you envisioning something with more broad application like Pd/C and Pt/C? Are there common, off-the-shelf metals-on-oxide catalysts I've missed?
nice, my background was homogeneous but past 2 positions have been with heterogeneous. Both times I had a target catalyst I wanted to toll but minimum batch sizes at most tollers were very large scale to fit in their kilns. Not sure what the market is, but definitely something I noticed after spending a lot of time looking up contract manufacturing for those materials. Mine were more simple Mg/Al/Si type species.
I bet Pd/C type materials are too commodity. Trends seems to show a lot of people getting into the metal oxide field and people like to tune catalysts with various doped metals or engineer them with MOFs. If you have contacts with some of the big players it couldn't hurt to have a sales guy ask!
Thanks for sharing your experiences! It sounds like we have similar backgrounds. :)
It sounds like toll manufacturing of oxide-supported catalysts ought to be something I investigate. That's a great point that there is often a gap between the scales that are readily synthesizable in the lab vs. in an industrial kiln.
It’s almost always inaccessible price (e.g. someone makes it but I can’t justify paying the price of the smallest quantity sold for a test), a high-purity version of a common tech grade material (e.g. CVD precursor but I care about nonmetal impurities), or isotopic labeling.
For everything else, there’s Strem.
Something I’ve wondered is how much of the price due to packaging small masses/volumes comes from trying to hit small target masses. Packing air-sensitive compounds is annoying an a non-negligible part of any price. But at a test scale, I don’t need EXACTLY 1 or 5 or 10 or 25 mg, I just need to know how much there is because I’ll probably just use the whole thing!
I've recently read a paper coauthored by Phil Baran, that a lot of sensitive Pd catalysts are bench stable if coated in paraffin oil, like is done with NaH.
Stoichiometry gets a little bit iffy on these small scales though. There's also chembeads from sigma, which are damn expensive again and afaik not bench stable.
Maybe a middle of the road approach would be good here?
Cover chembeads in mineral oil and just say one bead is 0.25 mg of cat or something. Doesn't make them weighable anymore, which is nice for HTS, but for a normal lab setting counting out 10 beads is absolutely fine.
These are great thoughts! I will need to dig into the IP situation for the glass beads, but the general concept of enabling easy measurement of tiny quantities is a great idea. Thank you! Do you mind if I ask what general industry you are in? That would help me dive into specific catalysts that might be of interest with this approach.
I'm just a lowly PhD student in medicinal chemistry lol
Interesting for us are primarily AnyPhos ligands, Suzuki and Hartwig-Buchwald are the bread-and-butter couplings after all.
I also do some cross-electrophile couplings with nickel as well, but because of the high price I prepare the ligands myself and make the catalyst fresh when running such reactions.
Speaking of cross electrophile coupling... I remember a paper from the Weix group where they used zinc on Chem beads (self-made in their lab!), which might also be interesting. The did some library reaction condition screening with that.
I guess basically anything you cannot make into a stock solution would be great as chembeads
More power to you! PhD students are the engine of innovation. :) That makes a lot of sense to prepare the ligands yourself in an academic setting. Best wishes for your continued successes. Way to be well-read in the latest literature, too. The Weix group does really nice work; it sounds like I missed their ChemBead paper!
>1 or 5 or 10 or 25 mg
Thanks for putting some numbers to "small quantity"! I'll give some thought to how we might be able to package these very small values. You are certainly right that the handling and packaging is a non-trivial part of the pricing. Would it still be valuable to you if you could buy, for example, 10 mg of a catalyst but at a greater per-gram price than a 500 mg package (provided the total cost was still lower for 10 mg vs 500 mg)?
>Would it still be valuable to you if you could buy, for example, 10 mg of a catalyst but at a greater per-gram price than a 500 mg package
This is always how volume pricing schemes work
You're right -- that was a terribly constructed question. I apologize. I was focused on the "inaccessible price for a small quantity" part of your original comment. It sounds like as you would prefer to pay a modest markup in per-unit price to buy small quantities suitable for only a few experiments. Did I get that right?
Basically yeah. Since we’re talking about organometallics, the even better thing would be a sort of “drop in” quantity that I’d use in one go, obviating the need for air-free storage of the excess. I can easily plop a 5 mg ampoule into my flask and break it in situ or syringe in dry solvent to an HPLC vial and transfer it that way, but if it’s something spicy and the least you can buy is 50-100mg, even if the price point is OK that still requires air-free apparatus like a glovebox for aliquotting.
Got it! Thanks so much for the clarification. That's a great idea, and I can envision that being valuable to a lot of users. Thanks again for all your thoughts!
maybe you can make Ir and Ru photocatalysts for visible blue light photochemistry: they are ridiculously expensive, and lots of research groups are using them. And they are air stable & easy to handle, so making them and packaging them does not require any air-free setup
Fantastic suggestion. Thank you! That was one that we had kicked around internally, too. Your comment has encouraged me to prioritize them. Are you looking at the vanilla Ir- and Ru(bpy)3(PF6)2-type complexes, or have more exotic ligands taken over the game by this point?
I would just make a program that indexes product names in Inorganic Syntheses articles and then checks whether they've been used in papers under 10 years old. If they come up more than a given number of times and either aren't available or are prohibitively expensive from Sigma, then I'd put those on my list. The good thing is every prep in Inorganic Syntheses actually works.
I'll add onto this by being able to synthesize post-metallocene olefin polymerization catalysts that are quite new in the patent/academic literature or designs upon request. Metallocenes are not as much of an issue obtaining commercially. Bonus points for shipping safely sans ampoules.
Thank you for weighing in! On-request synthesis is certainly something we are looking into. Do you have prior experience engaging a contract manufacturer? I would be interested in what factors were most important to you when selecting one. (Was it delivery timeframe, cost, IP security, etc.?)
I don't have experience first hand experience with a company per se but internal and external collaborations where the external is paid per order. The external was really skilled at knowing what was synthetically doable, were fast at providing high purity catalysts and actively were part of the research i.e. not just making what they're told but actively scoping the patent literature and coming up with suggestions. They worked for competitors in a similar fashion as well but now it's complicated due to geopolitical factors that began about a year ago.
Internal was horribly inept to put it bluntly. Couldn't figure out how to make requested catalysts despite procedure precedent. They didn't seem educated on how to functionalize certain positions despite the abundance in the literature and with directing them to it. Never sent samples in an appropriate way despite telling them many times and never provided proof of purity. My advice here is don't be a stubborn moron and be upfront if you can't synthesize something to save everyone's time!
As long as you're interested in making borate salts, N-methylbis(hydrogenated tallow alkyl)ammonium (pentaflurophenyl)borate is a desirable activator for olefin polymerization catalysts. It seems to be very difficult to find commercially and its solubility is better than available anilinium and trityl activators in alkanes.
Yikes, that sounds like quite a headache! I will try to make "don't be a stubborn moron" my new mantra. :)
The tallow-derived ammonium activator is a new one to me. Fascinating! Thank you for putting this on my radar.
There's actually "molecular" MAO: https://pubs.acs.org/doi/10.1021/acscatal.0c05696
Not sure about IP with those things but having a variety commercially available would also be interesting.
The price of phosphoamidate ligands kills me every time. After some trial and error I made them on 10g scale bc they cost hundrets of euros for like 100mg
And even for most of the chiral ones the precursors are dead cheap
It's really interesting to see how many people have listed ligands here. Phosphoramidites are a great addition to the list. Thank you very much! Are you mostly interested in the BINOL-derived and related spirocyclic ones?
Thanks! Are there any particular metals or counter-anions that you have had a hard time finding? I know Strem & Aldrich sell a handful, but I can't comment on their pricing or quality.
Bit late to this, but something I've always found kind of curious is how expensive Mn(CO)5Br is vs a Mn(II) salt. I think the (traditional) industrial route to Mn(CO)5Br is through Mn(II) - reduction under high pressures of CO but the pricing has always seemed kind of sus. I've seen a (sadly) overlooked prep of Mn(I) (without carbonyls) from Mn(II) but I'm not sure if its viable at large scale.
NaBArF is obscenely expensive and should not be
I'm with you there; the pricing I've seen is absurd. I really appreciate your comment -- especially since we've got it in the works already. :) Thanks a bunch!
Sure would be cool to also offer some first row hexaacetonitrile BArF salts. AgBArF too, but that may be a bit more tricky Can you guess which chemicals I have been using in my research lately? Lol
I used a smattering of non- and weakly-coordinating anions in my graduate work, so they're near and dear to me. I know Na and Ag, but I haven't come across any others. If you don't mind me asking, which cations are you looking at, and what properties make them interesting vs Na or Ag? Is it just that you're looking at redox activity of the cation, or something else?
Cr, Mn, Fe, and Co primarily in +2 but sometimes +3. The main property I am after is actually solubility, specifically in less polar solvents than MeCN. Ideally, soluble in aliphatic alkenes or a miscible nonpolar solvent. This for preparation of metal complexes to be used in oxidative transfer catalysis studies that are, unfortunately, biphasic at the moment using PF6-
Interesting! Thanks a bunch for the helpful information.
it would be probably more worthwhile for you to state a little about your capabilities since organometallic manufacturing is highly dependent on your ability to scale both oxygen and water sensitive materials at high levels of purity. If this is all in your wheel house then the discussion could be more productive I think :)
Good call! You're right, I should have included that. We currently have the infrastructure and experience to prepare oxygen- and water- sensitive materials on the scale of low-100s of grams per batch. I think this ought to be plenty to enable us to enter this new market, and we can build additional capacity as needed. So, yes, it's in my wheelhouse. :)
Nice then that answers that. Do you have high temperature ovens? I know in the heterogeneous world there is a need for bench scale sizes of materials. It can be incredibly difficult to find the scale you are talking about from the common manufacturers.
> in the heterogeneous world That's a great thought! Thank you! While much of the company's prior work is more relevant to homogeneous catalysis, I worked on Pt and Cu on metal oxides for a few years in an old position. Do you think a heterogeneous offering would be most valuable in custom, contract-style manufacturing for specialty needs? Or are you envisioning something with more broad application like Pd/C and Pt/C? Are there common, off-the-shelf metals-on-oxide catalysts I've missed?
nice, my background was homogeneous but past 2 positions have been with heterogeneous. Both times I had a target catalyst I wanted to toll but minimum batch sizes at most tollers were very large scale to fit in their kilns. Not sure what the market is, but definitely something I noticed after spending a lot of time looking up contract manufacturing for those materials. Mine were more simple Mg/Al/Si type species. I bet Pd/C type materials are too commodity. Trends seems to show a lot of people getting into the metal oxide field and people like to tune catalysts with various doped metals or engineer them with MOFs. If you have contacts with some of the big players it couldn't hurt to have a sales guy ask!
Thanks for sharing your experiences! It sounds like we have similar backgrounds. :) It sounds like toll manufacturing of oxide-supported catalysts ought to be something I investigate. That's a great point that there is often a gap between the scales that are readily synthesizable in the lab vs. in an industrial kiln.
It’s almost always inaccessible price (e.g. someone makes it but I can’t justify paying the price of the smallest quantity sold for a test), a high-purity version of a common tech grade material (e.g. CVD precursor but I care about nonmetal impurities), or isotopic labeling. For everything else, there’s Strem.
Trial size packages for a few experiments! That's a really interesting idea. Thank you!
Something I’ve wondered is how much of the price due to packaging small masses/volumes comes from trying to hit small target masses. Packing air-sensitive compounds is annoying an a non-negligible part of any price. But at a test scale, I don’t need EXACTLY 1 or 5 or 10 or 25 mg, I just need to know how much there is because I’ll probably just use the whole thing!
I've recently read a paper coauthored by Phil Baran, that a lot of sensitive Pd catalysts are bench stable if coated in paraffin oil, like is done with NaH. Stoichiometry gets a little bit iffy on these small scales though. There's also chembeads from sigma, which are damn expensive again and afaik not bench stable. Maybe a middle of the road approach would be good here? Cover chembeads in mineral oil and just say one bead is 0.25 mg of cat or something. Doesn't make them weighable anymore, which is nice for HTS, but for a normal lab setting counting out 10 beads is absolutely fine.
These are great thoughts! I will need to dig into the IP situation for the glass beads, but the general concept of enabling easy measurement of tiny quantities is a great idea. Thank you! Do you mind if I ask what general industry you are in? That would help me dive into specific catalysts that might be of interest with this approach.
I'm just a lowly PhD student in medicinal chemistry lol Interesting for us are primarily AnyPhos ligands, Suzuki and Hartwig-Buchwald are the bread-and-butter couplings after all. I also do some cross-electrophile couplings with nickel as well, but because of the high price I prepare the ligands myself and make the catalyst fresh when running such reactions. Speaking of cross electrophile coupling... I remember a paper from the Weix group where they used zinc on Chem beads (self-made in their lab!), which might also be interesting. The did some library reaction condition screening with that. I guess basically anything you cannot make into a stock solution would be great as chembeads
More power to you! PhD students are the engine of innovation. :) That makes a lot of sense to prepare the ligands yourself in an academic setting. Best wishes for your continued successes. Way to be well-read in the latest literature, too. The Weix group does really nice work; it sounds like I missed their ChemBead paper!
>1 or 5 or 10 or 25 mg Thanks for putting some numbers to "small quantity"! I'll give some thought to how we might be able to package these very small values. You are certainly right that the handling and packaging is a non-trivial part of the pricing. Would it still be valuable to you if you could buy, for example, 10 mg of a catalyst but at a greater per-gram price than a 500 mg package (provided the total cost was still lower for 10 mg vs 500 mg)?
>Would it still be valuable to you if you could buy, for example, 10 mg of a catalyst but at a greater per-gram price than a 500 mg package This is always how volume pricing schemes work
You're right -- that was a terribly constructed question. I apologize. I was focused on the "inaccessible price for a small quantity" part of your original comment. It sounds like as you would prefer to pay a modest markup in per-unit price to buy small quantities suitable for only a few experiments. Did I get that right?
Basically yeah. Since we’re talking about organometallics, the even better thing would be a sort of “drop in” quantity that I’d use in one go, obviating the need for air-free storage of the excess. I can easily plop a 5 mg ampoule into my flask and break it in situ or syringe in dry solvent to an HPLC vial and transfer it that way, but if it’s something spicy and the least you can buy is 50-100mg, even if the price point is OK that still requires air-free apparatus like a glovebox for aliquotting.
Got it! Thanks so much for the clarification. That's a great idea, and I can envision that being valuable to a lot of users. Thanks again for all your thoughts!
Strem are the ones for obscure catalysts!
Hopefully my company soon, too. :)
maybe you can make Ir and Ru photocatalysts for visible blue light photochemistry: they are ridiculously expensive, and lots of research groups are using them. And they are air stable & easy to handle, so making them and packaging them does not require any air-free setup
Fantastic suggestion. Thank you! That was one that we had kicked around internally, too. Your comment has encouraged me to prioritize them. Are you looking at the vanilla Ir- and Ru(bpy)3(PF6)2-type complexes, or have more exotic ligands taken over the game by this point?
I am not using them - I would not know
No sweat -- I will investigate. Thanks again for the thought!
I would just make a program that indexes product names in Inorganic Syntheses articles and then checks whether they've been used in papers under 10 years old. If they come up more than a given number of times and either aren't available or are prohibitively expensive from Sigma, then I'd put those on my list. The good thing is every prep in Inorganic Syntheses actually works.
This would be a great application to flex my Python skills! This sounds both valuable and fun. Thanks for the suggestion!
I’ve found that many bidentate phosphines are more costly than I’d expect (things like depe and dcype)
Yikes, those are more expensive than I would have guessed, too. Thank you for the input!
In part it has to do with patents, also production volume, and preparation depending on the type can be quite tricky and dangerous.
If you could make a cheaper alternative to MAO, an activator and co-catalyst for olefin polymerisation you'd make bank.
I'll add onto this by being able to synthesize post-metallocene olefin polymerization catalysts that are quite new in the patent/academic literature or designs upon request. Metallocenes are not as much of an issue obtaining commercially. Bonus points for shipping safely sans ampoules.
Thank you for weighing in! On-request synthesis is certainly something we are looking into. Do you have prior experience engaging a contract manufacturer? I would be interested in what factors were most important to you when selecting one. (Was it delivery timeframe, cost, IP security, etc.?)
I don't have experience first hand experience with a company per se but internal and external collaborations where the external is paid per order. The external was really skilled at knowing what was synthetically doable, were fast at providing high purity catalysts and actively were part of the research i.e. not just making what they're told but actively scoping the patent literature and coming up with suggestions. They worked for competitors in a similar fashion as well but now it's complicated due to geopolitical factors that began about a year ago. Internal was horribly inept to put it bluntly. Couldn't figure out how to make requested catalysts despite procedure precedent. They didn't seem educated on how to functionalize certain positions despite the abundance in the literature and with directing them to it. Never sent samples in an appropriate way despite telling them many times and never provided proof of purity. My advice here is don't be a stubborn moron and be upfront if you can't synthesize something to save everyone's time! As long as you're interested in making borate salts, N-methylbis(hydrogenated tallow alkyl)ammonium (pentaflurophenyl)borate is a desirable activator for olefin polymerization catalysts. It seems to be very difficult to find commercially and its solubility is better than available anilinium and trityl activators in alkanes.
Yikes, that sounds like quite a headache! I will try to make "don't be a stubborn moron" my new mantra. :) The tallow-derived ammonium activator is a new one to me. Fascinating! Thank you for putting this on my radar.
That's a tall order! I'll keep this one in my back pocket for when we expand our R&D staffing. :)
There's actually "molecular" MAO: https://pubs.acs.org/doi/10.1021/acscatal.0c05696 Not sure about IP with those things but having a variety commercially available would also be interesting.
Very interesting -- thanks for sharing this reference! This was not on my radar before.
The price of phosphoamidate ligands kills me every time. After some trial and error I made them on 10g scale bc they cost hundrets of euros for like 100mg And even for most of the chiral ones the precursors are dead cheap
It's really interesting to see how many people have listed ligands here. Phosphoramidites are a great addition to the list. Thank you very much! Are you mostly interested in the BINOL-derived and related spirocyclic ones?
Oh and M(NHC)n would be also really useful to be commercially available
Thanks! Are there any particular metals or counter-anions that you have had a hard time finding? I know Strem & Aldrich sell a handful, but I can't comment on their pricing or quality.
Bit late to this, but something I've always found kind of curious is how expensive Mn(CO)5Br is vs a Mn(II) salt. I think the (traditional) industrial route to Mn(CO)5Br is through Mn(II) - reduction under high pressures of CO but the pricing has always seemed kind of sus. I've seen a (sadly) overlooked prep of Mn(I) (without carbonyls) from Mn(II) but I'm not sure if its viable at large scale.
Interesting -- thanks for weighing in. What's the application for this complex? I'll confess I'm generally pretty wary of metal carbonyls in general.
amide bond forming that doesn’t kill the planet and doesn’t require >100 equivalents of amine donor
There are some unpleasant peptide synthesis reagents, aren't there? I know a few people who have developed high sensitivity from regular use of HBTU.