Big Fish, New Ponds?

Have you kept your ear to the ground? Felt something on the breeze? Getting a "gut feeling"?

The most recent edition of Chemistry Bumper Cars - Faculty Moves, for the uninitiated - leans towards bigger deals and dramatic poaches as the Fall term looms over the Summer horizon. Here's the latest I've heard about, with my own opinion about whether the rumor holds water.

Dave MacMillan to leave Princeton, for...?
Odds: Low

I hear what you're saying: MacMillan has already moved twice (Berkeley -> Caltech -> Princeton), and we're talking about a researcher who averages an award every year and a new named professorship every four. However, he's fairly well settled into a tight relationship with Merck, who are local to NJ. He's also helped propel Princeton back up in the rankings over the past decade. I can think of only one university that sounds like any kind of a step up, and they have plenty of organic power at the moment.

Dirk Trauner to NYU
Odds: Medium

Though I've heard this more than once, I'm scratching my head about how it makes sense for Trauner. Part of his motivation in returning to LMU was to continue the Mulzer mystique: the powerhouse European natural products group that makes densely-functionalized products appear as if by magic. Then again, NYU seems to be aggressively searching for a certain kind of chemist; maybe Dirk is slated to be the new Phil Baran of the East Coast?*

Update: As seen in the comments, Dirk himself confirms. My gracious thanks to the Professor.

Tom Rovis to Columbia
Odds: Certain

Signed, sealed, and delivered to Columbia back in the Spring.

Dave Liu to Broad from Harvard
Odds: Low

First he was an undergraduate wunderkind with Corey, now one of the youngest Full Professors and an HHMI scholar, all before age 40. He's already a core faculty member with Broad while managing his Harvard group, and I see no reason for Harvard (or for Liu) to wish to terminate his current position. This may sound like wild speculation or stargazing, but I fully suspect Liu's name goes on a nomination for a Big Prize within ~5 yrs, and I think Harvard would do everything they could to keep him in the fold for that day.

Update: As noted in the comments, does appear Liu will have to be physically present on the Broad's campus.

Karen Goldberg to leave U. Washington
Odds: Low

I very much want to believe, especially since UW lost Jim Mayer a few years back, that they can retain Goldberg, a C-H activation and general OM superstar. She boasts a local Center and a named professorship, as well as a Department with plenty of talented young blood: Boydston, Bush, Cossairt, Fu, Lalic, Schlenker, Theberge, Zalatan, all hired in just the last 6 years, doubtless some drawn there through her influence. I'm sure she'd succeed at a Caltech or an MIT, but I really don't know enough about her motivations to say any more conclusively.

Greg Verdine leaves Harvard to run companies full-time 
Odds: High

It's said you can throw a rock in Cambridge these days and hit a VC. Seeing how much apparent fun and success Verdine has had with his previous ventures into the private sector, I'm betting he continues this line full-time and slowly winds down managing theses and group meetings.

--
*Today's ridiculous statistic: In the past 20 years, Baran and Trauner have authored a combined 372 research papers. That's 2-3 entire careers, and these are guys with 20+ years ahead of them. Damn.

Counterion Conundrum

(For Popkin's great Science News writeup, click here)
(Update - Also, Chemistry World!)

Update (11/13/13) - Blog buddy Lila Guterman of Science News has the inside scoop:
"An answer! Authors via @gabrielpopkin: cerium(III)chloride heptahydrate (99.9% pure) from Sigma (cat. nr. 228931-25G)"

~~

Fascinating news for the inorganic biochemistry fans out there: Scientists have ID'd a bacterium (Methylacidiphilum fumariolicum) living in highly acidic volcanic pools that seems to use rare earth metals in one of its enzymes. A multinational team modeled the enzyme with a variety of rare earth cores, and the bacterium appeared to selectively take them up in cell culture. Cool!

Just one small problem: What's the counterion?!?

My crack online reporting team has scoured the manuscript, finding only mentions of a mysterious Ce(III), along with triply-oxidized La* and Pr. Nowhere in the Supporting Information do they mention reagents used, and the reporter has confirmed that this subject wasn't broached.

Given the other salts the researchers added to the media, it's likely that they used either cerium (III) sulfate or cerium (III) chloride. However, Sigma-Aldrich sells no less than 10 different cerium (III) salts (Strem has over 20!), and I'm willing to bet they have markedly different bioavailability, oxidation potential, aqueous solubility...the works.

Readers, does anyone know what the cerium source is in this paper?** I certainly don't wish to draw unwarranted conclusions, but we're all still touchy over another recent dust-up having to do with a miraculous trace element.

Please let me know in the comments.

*IUPAC police: Throughout the paper, the authors refer to "Ln ions." Do you suppose they mean La (lanthanum)? Are elements abbreviated differently in other places?

**Interestingly, the authors note that their acidic growth media leached trace rare earths out of the glassware. I've never looked at that as a reaction contaminant, but I guess I'll have to start!

Precious Serendipity

Serendipity often drives scientific inquiry.

Ask a famous scientist - Feynman, Archimedes, Fleming, to name a few beneficiaries - they'd tell you it's better to be lucky than good. But Pasteur's paraphrased "Fortune favors the prepared mind" spells things out more clearly; diving into the nitty-gritty of chemical transformations often brings up a chance pearl of wisdom.

Such is the case for a recent JACS ASAP, out of the Wang group at Xiamen University in China. Let's set the stage: the scientists attempt to create a stabilized bimetallic cluster compound from gold, silver, and hemilabile P-N ligands. When the starting Ag-Au complex meets acetonitrile and methanol, something interesting occurs: a dimeric crystalline compound forms, bridged by two fully deprotonated acetonitriles!

Those golden pyramids are pretty schnazzy.
Source: JACS | Wang group

So, why am I so excited?

1. That's a CCN (3-) anion stuck in there! What if you could, say, build a tetra-substituted carbon center just by adding electrophiles in sequence?

2. C-H activation of sp3 bonds = hard. Especially at room temp.
Well, there's (technically) 6 sp3 C-H bonds missing in that complex!

3. The authors note that water forms as the reaction progresses. Most nitriles, in the presence of Au/Ag catalysts and water, will hydrate to form amides. Not so here.

4. The authors point out that a gold oxo intermediate must be present for the cluster to form. They also point out that similar gold oxo catalysts (and silver oxide bases) pop up in the literature. Perhaps crazy intermediates like this commonly arise in gold-catalyzed reactions?

The best part? Studies like this always leave you with more questions than answers.
Perfect fodder for future projects.