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DBL%20Hendrix%20small.png College chemistry, 1983

Derek Lowe The 2002 Model

Dbl%20new%20portrait%20B%26W.png After 10 years of blogging. . .

Derek Lowe, an Arkansan by birth, got his BA from Hendrix College and his PhD in organic chemistry from Duke before spending time in Germany on a Humboldt Fellowship on his post-doc. He's worked for several major pharmaceutical companies since 1989 on drug discovery projects against schizophrenia, Alzheimer's, diabetes, osteoporosis and other diseases. To contact Derek email him directly: derekb.lowe@gmail.com Twitter: Dereklowe

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May 12, 2010

A Quick And Nerdy Question

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Posted by Derek

As a brief followup to my "Elements I Have Yet to Use" post, I note this new paper on cleavage of molecular nitrogen by a hafnium complex. And to get right down to organic synthesis, here's a paper from last year that used hafnium triflate as a Lewis acid.

OK, here goes: has anyone out there ever used hafnium for anything? Anything at all? I sure haven't. (N.b. - ordering some on purpose to raise your desktop monitor or prop the door open does not count).

Comments (28) + TrackBacks (0) | Category: Life in the Drug Labs


COMMENTS

1. Ron on May 12, 2010 12:20 PM writes...

My lab regularly uses zirconium and hafnium complexes as catalysts for olefin polymerization. I realize this isn't within the scope of organic synthesis, though.

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2. Anonymous on May 12, 2010 12:25 PM writes...

Does device manufacture count? It makes an impressive dielectric, which is a critical need to keep Moore's Law going. Figuring out how to deposit and etch it, though, is non-trivial. There's some hafnium chemistry for you.

Permalink to Comment

3. gmz on May 12, 2010 12:30 PM writes...

I recall a few years back (late 80s, early 90s) Suzuki used Hafnocene catalysts for the synthesis of aryl glycosides from glycosyl fluorides:
http://old.iupac.org/publications/pac/1994/pdf/6607x1557.pdf

Permalink to Comment

4. josh on May 12, 2010 12:30 PM writes...

i did some rauhut currier stuff at the beginning of my grad school experience, dimerizing substituted enones with PR3. Hafnium triflate worked pretty well to up the yield.

Permalink to Comment

5. John Spevacek on May 12, 2010 12:51 PM writes...

HfO is to calibrate UV spectophotometers.

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6. David on May 12, 2010 12:54 PM writes...

You probably use it every day, in your computer. Most Intel chips using the 45 nm transistors and smaller (most core2 and newer) use hafnium or hafnium oxide gates.

Someone in my advanced instrumental analysis class wanted to run some ICP-AES on components of a circuitboard, and used some as a reference.

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7. CMCguy on May 12, 2010 1:13 PM writes...

#1 Ron why do you think "olefin polymerization" "isn't within the scope of organic synthesis"? I have always considered the production of polymers one of the greatest applications and benefits of organic chemistry. Admittedly classical training of Syn types rarely include polymers (on purpose at least) and most Polymer chemists seem grown more from P-chem types (my exposure). There is some fairly sophisticated organic chemistry that can go on and certainty the focus is often toward huge scales by cheap and reliable means but do not discount because is not pharma oriented.

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8. John on May 12, 2010 1:24 PM writes...

Picking the right Lewis acid catalyst for alkylation of a ketene silyl acetal is the same sort of black box excercise as picking the right palladium catalyst for a Suzuki reaction.

I don't remember if it was hafnium triflate in particular, but I remember that one of those lanthanide triflates was the magic catalyst for a reaction I did a few years back.

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9. Anonymous on May 12, 2010 1:46 PM writes...

Yamamoto used hafnium triflate to catalyze a Fisher esterication reaction at rt in a ~2000 Science paper.

Permalink to Comment

10. CanChem on May 12, 2010 1:58 PM writes...

We had tried a number of experiments with Hf in a superconducting supercollider to explore the potentials for extreme trans-uranic elements. Unfortunately we found that it wasn’t amenable to nuclear fusion; crashing a pair together never gave anything but Ho.

(too nerdy?)

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11. Larry on May 12, 2010 2:02 PM writes...

We have used it to prepare organometallic complexes for the electronics industry. It is fairly common there.

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12. James on May 12, 2010 2:11 PM writes...

We use it (as Cp2HfCl2)pretty regularly as a promotor for glycosyl fluorides. Does a proper job.

Permalink to Comment

13. processchemist on May 12, 2010 2:25 PM writes...

In scaled up glycochemistry Hf never showed up in my experience (I have to say that glycosyl fuorides too are the less popular halosugars on scale, and that on the lewis acid front Ag and Hg tend to vanish quickly).

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14. RandDChemist on May 12, 2010 2:52 PM writes...

Yes, as a Lewis Acid catalyst.

Permalink to Comment

15. LMM on May 12, 2010 3:11 PM writes...

I'm with Ron -- it's often used in modern olefin polymerization catalysts.

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16. Vader on May 12, 2010 3:38 PM writes...

It makes nice nuclear reactor control rods.

... You did say "Anything at all?"

Permalink to Comment

17. Reality check on May 12, 2010 4:35 PM writes...

Hey Derek – Instead of writing crybaby articles on maitotoxin and synthesis (which actually do something tangibly good for humanity), why not question this kind of rampant junk science fueled by taxpayer money that makes up most of the journals these days:

http://pubs.acs.org/cen/news/88/i20/8820notw1.html

nanoscience = the great hoax of our generation

Permalink to Comment

18. Phil on May 12, 2010 6:32 PM writes...

Of the many things wrong with your post, I'll point out that nanotechnology is on the way to solving many problems, including EV batteries.

http://nobelprize.org/nobel_prizes/physics/laureates/2009/index.html

I'll also say that every field of science is full of bozos doing stupid things with taxpayer money that will never yield anything useful. Only a few of these bozos actually know that their work is useless.

Also, many seemingly useless discoveries have been unearthed at some later time. Boolean logic comes to mind. It was an invention that in the middle of the 19th century seemed a complete waste of time, and now comprises the basis of computer programming.

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19. Phil on May 12, 2010 6:44 PM writes...

Gah, I wish I could edit my previous post. Here is a link that is actually about nanowire batteries.

http://www.nature.com/nnano/journal/v3/n1/full/nnano.2007.411.html

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20. Mitch on May 12, 2010 7:58 PM writes...

I made some hafnium oxide thin films. Here is a link to the paper.

http://dx.doi.org/10.1016/j.tsf.2007.11.127

Permalink to Comment

21. Sili on May 13, 2010 4:22 AM writes...

nanoscience = the great hoax of our generation
Don't be silly. Global Warming is the great hoax of our generation. Get with the programme. Permalink to Comment

22. artemis on May 13, 2010 8:34 AM writes...

yeah we use it as a lewis acid for asymmetric Diels-Alder reactions.

Permalink to Comment

23. Hap on May 13, 2010 8:40 AM writes...

What is maitotoxin going to do for humanity (other than, perhaps, delete a tiny bit of it)? Its synthesis might do something for humanity, but considering past history, probably not (neither of the proximate analogies, the syntheses of palytoxin and brevetoxins, did a whole lot - taxol's synthesis did something significant, though not KCN's version (unless you count the pressure imparted on Holton's synthesis)), and it's going to cost an awful lot of money to do. I think you need to ease back on the crack a bit.

On the other hand, I get tired of seeing the "look at the tiny pretty shapes I can make in [various toxic metals or their salts]" papers in JACS, ACIE, etc.

Permalink to Comment

24. Phil on May 13, 2010 11:04 AM writes...

This thread just made me think about how I haven't seen a Bucky Ball in the literature recently. So glad that nonsense it over (knock on wood).

Permalink to Comment

25. cookingwithsolvents on May 13, 2010 2:57 PM writes...

made some Zr, Hf compounds to have M-L complexes w/ relatively redox-inactive metal sites (needed 4+ so Zn was out). Pretty user-friendly metals...nice crystalline compounds even if they were all white/colorless. :(

@24

Check the organic photovoltaic literature...they are alive and well.

Permalink to Comment

26. MR on May 14, 2010 12:46 AM writes...

@25
Well there is graphene and carbon nanotubes. How are those going?

Of course, artificial asbestiform serpentine (crysotile) might be worth looking into. Could be easier to make longer, stronger fibers with it than with CNTs. I also wish any potential researchers good luck in obtaining a research grant for something like the manufacture of synthetic asbestos.

Permalink to Comment

27. Anon on May 14, 2010 11:16 AM writes...

Hf can be used much like Ti, Zr, Nb, etc to do reductive coupling of unsaturated organics

Permalink to Comment

28. dvrvm on May 15, 2010 2:53 AM writes...

@Phil #24: A lab I worked in briefly seems to be getting out of the buckyball business, I think that's the general trend currently. I never quite got what people wanted to do with them in the first place, besides of being interesting structures in the context of theoretical carbon chemistry...

Permalink to Comment

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