ChemBark

ChemBark has learned that superstar inorganic chemist Daniel Nocera is moving from MIT to Harvard. Eric Jacobsen, chairman of the Department of Chemistry and Chemical Biology at Harvard, announced the news today by e-mail:

Dear Members of the CCB Community,

I am very pleased to share some very good news: Dan Nocera, one of the world’s leading inorganic chemists and a major figure in energy-related research, will be moving with his group to our department this Fall.

During his career at Michigan State University and more recently at MIT, Prof. Nocera has done ground-breaking work in the activation of small molecules such as oxygen and water by designed inorganic complexes.  He and his group are particularly interested in finding practical ways to harness the sun’s energy, with obvious implications for global energy production and storage.  The following press release describes some of his most recent work: http://web.mit.edu/newsoffice/2011/artificial-leaf-0930.html

The new Nocera labs will be located on the third floor of Conant, and a major renovation of that space will be taking place between now and the expected arrival of the group in the Fall.  I hope you will join me in doing everything possible to welcome the Nocera group when they arrive, and to make their move down Mass Ave as pleasant as possible.

Sincerely,

Eric Jacobsen

For many years, inorganic chemistry at Harvard began and ended with the magnificent Dick Holm. There simply were no other true inorganic professors, and when he semi-retired, Harvard was left with a gaping hole in its faculty. For years, rumors swirled that several lucrative overtures made to inorganic professors at MIT were rebuffed. In fact, the pendulum swung so far the other way that MIT nearly poached Jacobsen from Harvard. Questions still linger over how MIT was left standing at the altar.

Nocera positions himself within a herd of inorganic chemists, possibly to avoid capture by poachers from Harvard. January 2012 - Huntington Beach, California

In Nocera, Harvard has finally purchased a star. He instantly elevates inorganic chemistry on Oxford Street to a top or second-tier program. The school also now seems in a much stronger position to solidify its program from both the top (with other senior hires like Nocera) and bottom (with junior-faculty searches specifically targeted at making inorganic hires like young star Ted Betley). It will be interesting to see how Nocera and Betley work together; Betley was a postdoc under Nocera at MIT.

So, score one for the Crimson. I hope the Nocera Group enjoys its shiny new (and historic) lab space.

Remember to follow @ChemBark on Twitter for breaking news that can’t wait for a proper full-length post on the blog. You may also read these tweets in the sidebar on the left of this page. If you have a news tip to share, please send it by e-mail. You will receive as little or as much credit as you desire.

The Chemmy Award for Organic Achievement of the Year goes to:

Melanie Sanford (Michigan) for establishing that Pd(IV) intermediates are important in at least one class of catalytic C–H bond activation reactions

I had decided on the recipient of this Chemmy a long time ago but procrastinated on writing the citation. This weekend, commenter “tuna fish” mentioned that Dr. Sanford might be moving to Yale or Caltech, and while I have no idea if this is true, the comment reminded me of my fondness for her work and that now is as good a time as any to write about it.

First off, trying to “contain” the Chemmy achievement awards in the various chemical disciplines to one year (here: 2006) is going to be difficult, because cool discoveries often take time to develop and get noticed. In this case, Sanford’s C–H activation work can be traced back to 2004. It was only last year, however, that the picture became clear (at least, clear to me).

When I learned organometallic chemistry—way back in 2002—we were essentially taught never to invoke Pd(IV) intermediates in our mechanisms.  Pd(IV) was simply too energetically-inaccessible to be relevant in most cases. Along these lines, I witnessed the merciless ridicule of more than one student by the teaching staff for using Pd(IV). Instead, good boys and girls used the Pd(0)/Pd(II) couple in their mechanisms.

In 2004, Sanford came along and published a simple case of catalytic, chelate-directed C–H bond oxidation:

Instead of outlining a mechanism that shuttled back and forth between Pd(0) and Pd(II), Sanford proposed a mechanism involving Pd(IV):

Naughty!  Or so I thought.  A subsequent study essentially extinguished all doubt that the Pd(IV) mechanism was correct. In this 2005 JACS comm., the Sanford crew hypothesized they could change the system to stabilize the Pd(IV) intermediate, found they could actually isolate it, got a crystal structure showing that it was indeed a Pd(IV) species, and then showed that heating it gave the same types of products that they saw in reactions where the intermediate could not be isolated. Crystal structures are the closest thing we can get to having incontrovertible photographic evidence of what molecules are actually doing, so you can’t really argue this one.  Score one for Pd(IV).

I know a lot of the hardcore synthesis crowd isn’t enamored with this sort of C–H activation chemistry because it is chelate-directed, which limits the scope of the reaction. That’s true, but what makes this batch of work so interesting is not the synthetic utility as much as the scientific value. We gained a new appreciation for the mechanism at play in these reactions and had to reassess a long-held notion of what isn’t reasonable.

So, congratulations to Dr. Sanford and coworkers. Enjoy your Chemmy and keep the good work coming.  And if any of you donkeys out there thinks there was someone else more deserving of this award, feel free to register chemmeow.com and start your own damn blog.

(more…)