New Paper Published on Organometallics ASAP

Our latest paper has just appeared on the ASAP page for the ACS journal Organometallics: “Computational Discovery of Stable Transition Metal Vinylidene Complexes”, DOI: 10.1021/om500114u, arising from my collaboration with Dr Jason Lynam at York. The Bristol part of the work was started by two summer students, Ben Rawe (now at UBC) and Tim King (now at Cambridge) and then continued by a final year undergraduate project student, Keshan Bolaky; the rest of the calculations were done by yours truly. In this work we have explored substituent, metal and ligand effects on the thermodynamic preference for the vinylidene tautomer with both experiment and computation. This has allowed us to formulate a “recipe” for the stabilisation of vinylidenes by transition metal complexes. If you don’t have institutional access, I’d be happy to share via ACS Articles on Request, please get in touch!

Table of Content Graphic, Reprinted with permission from {COMPLETE REFERENCE CITATION}. Copyright {YEAR} American Chemical Society.

Table of Content Graphic, Organometallics, Article ASAP, DOI: 10.1021/om500114u. Reprinted with permission from Organometallics. Copyright 2014 American Chemical Society.


Perennial Grass (Miscanthus)

From the Picture It… Chemistry blog.

Picture it...

Our society relies on oil. We use it to power our cars, our homes and our factories. Yet oil is formed over millions of years and one day it will run out. But what if we could grow plants to use as fuel? Could they take the place of oil? Welcome to the exciting, and controversial, world of biofuels.

1. This picture shows some leaves of the perennial zebra grass Miscanthus sinensis ‘Zebrinus’ in a measuring cylinder on the draining board of a laboratory sink, a small model of a section of lignin polymer, as well as a wash bottle of ethanol and a small bottle of petroleum ether, distilled to have a boiling point between 40 and 60 degrees Celsius. The zebra grass is standing in for one of its cousins, Miscanthus x giganteus, which is starting to be used as a source of renewable energy crop. This…

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From the archives – GRC on Organometallic Chemistry (July 2012)

View of the coast from Salve Regina University, Newport, Rhode Island

When Hurricane Sandy tore into the eastern seaboard of the US, I actually sought out the local news for Newport Rhode Island, as well as the university sites of several US colleagues to see whether they had been badly hit. I know that travel for conferences and meetings is considered, especially by members of my family, as one of the perks of the job (at which point incredulity is expressed if you mention that you haven’t been to visit all (any) of the highlights of not just the nearest city, but the entire country). And meanwhile, back in the real world, sometimes it just becomes a chore, especially if you haven’t been home for a while, or it’s hot and you end up sitting in lectures and meetings all day, deprived of both sleep and decent food.

View of the coast from Salve Regina University

But both points of view conveniently forget one thing – there is merit in travelling abroad for researchers as it’s often easier to connect with people in person, and that ranges from meeting somebody for the first time to discussing a long-term joint project, as well as from chatting over lunch with a distant colleague to completing a significant publication with your old boss. All of it is much easier (at least for me) if you are actually meeting the other party. So, despite being a fairly grumpy traveller, I tend to pack my suitcase several times every year and put my trust in conference organisers, airlines and hotels, to meet up with colleagues, friends and former students, and to catch up about work. And I usually come back not just with a backlog of work, but also with new ideas, new contacts and sometimes even with progress on papers that have been languishing on somebody’s desk until we had a chance to kick ideas around and get them done. A Skype call just can’t beat that.

I think this is the Columbia, winner of the 1958 America’s Cup

So in July this year, I went to the Gordon Research Conference on Organometallic Chemistry, which takes place every year in Newport, Rhode Island, on the campus of Salve Regina University. If you’ve never been, Gordon conferences have a slightly different format, with talks both in the morning and late afternoon/evening, but a few hours after lunch free for other activities. While it was nice to see the sun (and actually necessary to stave off jet-lag), I passed on football (sorry, soccer) and other sporty activities, and explored the local area on foot instead, as well as networking with colleagues in the breaks. I even managed to go “sight-sailing” – not as good as controlling the boat yourself, but at least an opportunity to get out on the water for a couple of hours. And the best bit – no guilt! No skiving required! And plenty to talk about, as you could always ask about afternoon activities as well as research interests. I even used some of the photos, as well as maps of both areas (Newport, UK and Newport, Rhode Island, USA) in my talk about “Prediction of Ligand Effects on Organometallic Catalysts”, which is all about maps (of ligand space) after all.

View of the bay at Newport, RI

Having made these personal connections with both site and people, I actually wanted to know whether anybody had been badly affected by Hurricane Sandy and whether the Salve Regina site, which is incredibly close to the sea as you can see in the photos, was still standing. So I’ll be dropping a line to some, and listen to the jungle drums about others. But, and this is my point, the important thing is there is now a personal connection, because I’ve been there. It is difficult, especially for students and early-career researchers, to meet colleagues on other continents and so make those broader connections. But it is worth doing because you can’t divide the world neatly into work and private life when work takes up most of your time and passion. Now I just have to remind myself of that next time planes or trains go wrong…

A schooner in the bay, Newport, RI


New Paper – LKB-PPscreen

Schematic showing the variables for bidentate ligands in organometallic catalysis.

As hot-off-the-press as online publishing ever gets, our latest paper has just become available online as a Dalton Transactions Advance Article:

Screening substituent and backbone effects on the properties of bidentate P,P-donor ligands (LKB-PPscreen).
In it, we present a computational exploration of the effect of systematic variation of backbones and substituents on the properties of bidentate, cis-chelating P,P donor ligands as captured by calculated parameters. The parameters used are the same as reported for our ligand knowledge base for bidentate P,P donor ligands, LKB-PP (Organometallics 2008, 27, 1372–1383; Organometallics 2012 31, 5302–5306), but calculation protocols have been streamlined, suitable for an extensive evaluation of ligand structures. Analysis of the resulting LKB-PPscreen database with principal component analysis (PCA) captures the effects of changing backbones and substituents on ligand properties and illustrates how these are complementary variables for these ligands. While backbone variation is routinely employed in ligand synthesis to modify catalyst properties, only a limited subset of substituents is commonly accessed and here we highlight substituents which are likely to generate new ligand properties, of interest for the design and improved sampling of bidentate ligands in homogeneous organometallic catalysis.
AKA the work of one hot summer where we decided to run as many calculations as we could get away with!