Reactions: Marshall Brennan

Marshall Brennan is an Associate Editor for Nature Chemistry. He blogs at Colorblind Chemistry and goes on Twitter by @Organometallica.

1. What made you want to be a chemist?

The path that brought me to chemistry is a little unusual. I actually began my undergraduate studies in journalism, not chemistry—it wasn’t until I found myself a little bored of the curriculum about halfway through my first year that I decided to focus on a science. I initially switched into chemistry to try and con my way into the physics department, but once I started in on general chemistry, I was hooked. I especially love the subtle logic of working out reaction mechanisms and understanding how molecular geometry influences macroscopic properties. Once I started in on chemistry, I never looked back!

2. If you weren’t a chemist and could do any other job, what would it be – and why?

I have often thought that, if I had to do it all again, I would be part of a natural products isolation group. I imagine the job isn’t as glamorous as I think it is, but the idea of spending summers diving in coral reefs and winters running purifications is wildly romantic to me.

3. What are you working on now, and where do you hope it will lead?

Well, I suppose I’m just getting started here at Nature Chemistry, so there’s a lot of uncharted territory for me. I’m looking forward to seeing what exciting new research the chemistry community has in store for me!

4. Which historical figure would you most like to have dinner with – and why?

This is the question I have come back to the most times in the course of this interview. At long last, I have to go ahead and default to my favorite historical chemist, Sir Edward Frankland. While relatively unknown, he made so many critical contributions to early bonding theory and synthetic organometallic chemistry. More importantly, his descriptions of his laboratory hijinks are a hilarious read and I would be delighted to use my time machine to hear about them directly.

5. When was the last time you did an experiment in the lab – and what was it?

It was just a few weeks ago—I was running screens to develop new C–C bond activation reactions. The work is somewhat tedious, but very rewarding. Being able to describe a new bond-forming reaction that no one has observed before is its own sort of thrill!

6. If exiled on a desert island, what one book and one music album would you take with you?

Tricky question! The music album is straightforward—I would have to go with “Your New Favourite Band” by The Hives. As for the book, that’s the tougher part… I might have to cheat a little and go with Franz Kafka’s collection of short stories. Kafka wrote some really chilling stories that seem more cerebral every time I read them, so that might help with preventing boredom on the desert island.

7. Which chemist would you like to see interviewed on Reactions – and why?

I would whole-heartedly recommend Prof. Gregory Girolami—in addition to carrying out some truly fascinating research, he’s a bona fide historian of chemistry and I have yet to have a conversation with him that isn’t captivating.

Another four bricks in the wall (part II)

Editor’s note: this post written by Shawn Burdette and Brett Thornton is a companion piece to the Commentary article ‘Another four bricks in the wall‘ published in the April 2016 issue of Nature Chemistry.

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If discovering and naming new elements was not complex enough, the discoverers must also propose a two-letter symbol. For reasons that are presumably related to adherence to tradition and historical precedent, IUPAC guidelines require two-letter symbols for new elements, with the first letter capitalized and the second lowercase. Although that sounds simple, in reality, finding a suitable symbol for a new element can be nearly as tricky as selecting a name.

Most of the figures for the commentary on the 4 new elements required making educated guesses about what element symbols would correspond with the hypothetical names. Element symbols, like element names, follow an arcane set of rules. Symbols that have been used in the past, but abandoned, may not be reused. Since there are only 114 named elements, some using single-letter symbols, and 26 × 26 = 676 possible two-letter combinations, there initially appears to be lots of available symbols to choose from. Upon further inspection though, problems start to arise.

Part of this symbol problem arises from most element names coming from Indo-European languages, and principally Germanic and Latin languages, which share many common phonemes. Put another way, there are limited numbers of ways to put together letters in English that make sense, and some letters appear far more frequently in element symbols than others – see the chart below:

Letter occurrence frequency in the first 114 assigned element symbols, as of March 2016.

Letter occurrence frequency in the first 114 assigned element symbols as of March 2016.

 
As more and more elements are added to the table, choosing ‘valid’ symbols becomes more difficult. In the case of copernicium, researchers originally proposed the symbol ‘Cp’. As was pointed out in a letter to Nature, Cp previously had been used to denote ‘cassiopium’, a competing name for lutetium in the early 1900s that had appeared on periodic tables. IUPAC ultimately changed the symbol to ‘Cn’ to prevent confusion. Astute readers will recognize that Cp is also used to abbreviate cyclopentadienyl anion, however, none of the IUPAC documents list this as a potential issue. Others have pointed out that Cn was the symbol for ‘coronium’, a widely discussed element in the late 1800s and early 1900s. Coronium, which turned out to be highly ionized iron in the solar spectrum, was never placed on the periodic table. Perhaps the restriction on reusing a symbol need not apply if the element was never assigned a spot.

The illustration for ‘japonium’, our guess for element 113, uses the symbol ‘Ja’. Using the first 2 letters of the proposed name was as an easy derivation because no other element symbol contains the letter ‘J’. If we had guessed ‘nipponium’ however, there would be a dilemma. The single letter ‘N’ is taken by nitrogen. Ni is nickel, Np is neptunium, No is nobelium, so the first combination that is unclaimed is ‘Nn’. There are no double-letter element symbols, so while this might look odd, there are no IUPAC restrictions that would prevent this combination. Alternatively, it would be a clever maneuver to integrate the more familiar exonym ‘Japan’ with the Japanese name for their country and propose Ja as the symbol for nipponium. There is certainly precedence for unmatched chemical symbols. Na and Ag for sodium and silver, from the Latin names natrium and argentum, for instance. However, using symbols from another language has not been applied to newly discovered elements since the early 1800s, unless one counts the long fight over W for tungsten.

In the illustration for ‘moscovium’, a similar problem arises. Mo is molybdenum, so ‘Ms’ would be next in line. Unfortunately, Ms is a common organic chemistry abbreviation for the mesyl functional group (methylsulfonyl), though it’s unclear if this would be an obstacle to the symbol. In the event that organic abbreviations are deemed problematic, ‘Mc’ would be the next choice. Mv was widely used as a symbol for mendelevium before Md was adopted as the official symbol (ref. 1), and therefore would be unlikely.

Likewise, Te is taken by tellurium, so ‘tennessine’ could be ‘Tn’. Until the mid-20th century though, IUPAC defined Tn as the symbol for the 220Rn isotope, a use that persists in current literature. ‘Ts’, the other possible symbol, is the abbreviation in organic chemistry for tosyl groups (p-toluenesulfonyl). This poses a quandary if tennessine is the chosen name for element 117; all the obvious symbols derived from letters in the name might be off limits. If single-letter symbols were resurrected, ‘T’ might work, except tritium uses that letter as a chemical symbol.

There are 14 single-letter symbols (H, B, C, N, O, F, P, S, K, V, Y, I, W, and U). That might suggest that 12 are still available for new elements, but some have already been taken. D and T, as mentioned above, are deuterium and tritium respectively. G was ‘glucinium’, a competing name for beryllium. ‘A’ was an early symbol for argon before it was changed to Ar (ref. 1). When einsteinium was named in the 1950s, the original symbol proposed was ‘E’, but this was changed by IUPAC to Es (ref. 1). ‘M’ is often any generic metal in chemical equations. ‘X’ is any halogen. ‘R’ is an organic functional group. ‘J’ is commonly used for iodine in German-speaking countries. By process of elimination with a 26 letter alphabet, that leaves only L, Q, and Z as unclaimed single-letters.

Ultimately, we guessed Tn for tennessine to agree with the postal code and familiar abbreviation of the state. IUPAC however might prefer Ts because the abbreviation for tosyl is less well-defined by IUPAC than Tn was for thoron.

In the illustration for ‘octarine’, the symbol ‘Oc’ was an easy selection since the only other ‘O’ elements are O (oxygen) and Os (osmium). Although the illustration of scientists doesn’t include symbols, we can still speculate about what might be chosen for these hypothetical element names. ‘Ghiorsium’ could easily claim ‘Gh’ as only germanium (Ge) and gallium (Ga) use the letter ‘G’. For moseleyon, or any element named for Henry Mosley, ‘Ml’ or ‘My’ have to be selected since Mo already belongs to molybdenum, Ms has the complications already discussed for moscovium, and Me is the common abbreviation for methyl. William Ramsay’s namesake ramsayon, would likely use ‘Rm’, ‘Rs’, or ‘Ry’ after passing over the already claimed Ra, which is used by radon. As with japonium, Jo and Jl are theoretically open for ‘joline’ since there are no ‘J’ elements; however, joliotium was suggested for element 102 (now nobelium) with the proposed symbol Jo in the late 1950s, and Jl for element 105 (now dubnium) by IUPAC in 1994. Would a ban on reusing symbols lead to Ji, Jn or Je being preferred?

While symbol speculation might not have the allure of guessing the actual name of an element, the ultimate choice is no less important. The chemical symbol is the ‘face of the franchise’ for each element; though element names may vary between languages, the symbols are universal. The initial encounter with an element for chemistry students is as likely to be the symbol as the name. So perhaps it’s not surprising, that at times, the choice of chemical symbol has been as controversial as the name itself. Well, almost as controversial.

References

1. IUPAC: Commission de Nomenclature de Chimie Inorganique, in ‘Comptes Rendus de la Dix-Neuvième Conférence, Paris’, 1957, p. 93.

ACS: Synthetic catalysts, not different, just better

I spent the early part of my first day in the metal-mediated reactions session. I particularly enjoyed a presentation by Andy Thomas from Scott Denmark’s group at UIUC, on rapid-injection NMR studies of Suzuki reaction intermediates.

Immediately after lunch I took a little bit of a trip down memory lane to attend the session on Lewis base catalysed asymmetric transformations and see a presentation by my PhD advisor Alan Spivey. It was genuinely fascinating to see the most recent achievements in areas that I spent a large chunk of my life battling. It’s gratifying to see some of these things really starting to work out. The presentation immediately following this was by Adam Kamlet from Pfizer. He described the use of a chiral DMAP catalyst to effect a dynamic kinetic resolution of a series of tetrazole containing prodrugs. The juxtaposition of these two talks really brings home that these studies are more than just an academic exercise, and I think it’s fair to say that Alan’s talk has inspired some future experiments for Adam.

In the second part of the afternoon I moved to hear Matt Sigman talk on the use of big data in physical organic chemistry. The topic really gets to the heart of what I believe many who work on new reaction methodology would like to do: correlate simple physical parameters of catalysts/ligands to reaction outcomes like rate and selectivity. As Matt pointed out early in his talk it’s all about trying to understand the outliers and all too often these results end up buried in supporting information or ignored altogether. This is of course not the recommended course of action.

Matt was talking in an award symposium (The ACS award for creative work in synthetic organic chemistry) honouring Scott Miller. In his award address, Scott spoke about his development of low molecular weight peptide catalysts for a whole variety of asymmetric reactions. I particularly enjoyed his definition of a complex molecular environment (a widely used term) as “any system in which your current reaction design isn’t working”.

A question Scott posed towards the end of his talk had me thinking for a while. I tried to tweet about this but wasn’t easy to explain in 140 character bursts, so I’ll try again here: In the early 2000s Miller and his group reported peptide catalysts for the phosphorylation of meso myo-inositol-derived triol ($). They were able to identify catalysts for selective functionalization of either the 1- or the 3-hydroxyl groups, a fantastic achievement and my inspiration for the somewhat tongue-in-cheek title of this post (a play on the title of a review article from Nature in 1991).

What they didn’t develop — possibly because they weren’t trying — was a catalyst to phosphorylate the 5-hydoxyl group. This would be a meso-to-meso transformation and thus, Miller suggested, wouldn’t have been considered of interest by the editors of leading journals, despite being possibly the most challenging transformation. I wouldn’t have rejected it of course as I was only a PhD student at the time (notice how I squirmed out of that one?). I do think he’s right though and I agreed with another editor (from a top journal that I won’t name) such a transformation would likely have been rejected without review!

Well, it’s Monday morning here in San Diego, so it’s time to head off to some more sessions – I hope it’s as enjoyable as yesterday.

Steve

Stephen Davey (Chief Editor, Nature Reviews Chemistry)

The 5th Molecular Sensors and Molecular Logic Gates Meeting

Editor’s note: this is a guest post on behalf of Prof. Tony James.

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We are very excited about the upcoming 5th Molecular Sensors and Molecular Logic Gates (MSMLG) meeting in Bath from July 24th to 28th 2016. The MSMLG Award Lecture will be delivered by inspirational scientist and good friend Eric V. Anslyn. With great ‘Sense and Sensibility’ Eric was the unanimous choice of the Molecular Sensor and Logic Community for the 2016 MSMLG award.

We are delighted that the meeting includes a special conceptual lecture by Sir J. Fraser Stoddart (Sponsored by Chem from Cell Press) a founder of logic in chemistry and inspiration to many of the researchers at the meeting. We will then be treated to an Irish adventure by AP de Silva (Nature Chemistry Lecture) who will shed light and amuse us with his many important research stories based on his Sri Lankan origins a touch of serendipity and driven by friendship.

The meeting will be a true ’round table’ of exciting and delightful research by an unparalleled line-up of scientists from the molecular sensing and logic community. Held at the University of Bath during its 50th Anniversary in the delightful World Heritage City off Bath. For those wishing to attend the meeting registration will remain open till the 18th July 2016. For more information contact Tony James and Dan Pantos (www.msmlg2016.uk, msmlg2016@bath.ac.uk)