Dr Alan R Kennedy

Dr Alan R Kennedy

Contact Details

Room No. R617
Telephone +44 (0)141 548 2016
Fax +44 (0)141 548 0876
email a.r.kennedy@strath.ac.uk

Biography

For Reductionists

Publications 269

h-index       28

Academic since 2001

Current harassment level  approx. 87%

For Those Who Prefer Words

Background

I received both my first degree and my PhD from the University of Glasgow, the later was in the synthesis and structure of organometallic (Rh, Ni, Pd) complexes and was supervised by Drs Ron Cross, Ken Muir and Lj. Manojlovic-Muir.

It soon became apparent that the ability to stick P to Rh (often in yields as high as 15%) was not a skill sought by prospective employers and so as the years passed I have moved more towards structural and crystallographic chemistry.

I've held various post-doctoral type posts at both the University of Glasgow and across town at the University of Strathclyde and spent too much time at synchrotron sources.

During this period I set up Strathclyde's first single crystal X-ray diffraction laboratory and later the joint Glasgow/Strathclyde Crystallography Laboratory.

Eventually Strathclyde decided to keep me, and since 2004 I've been a full member of lecturing staff in the inorganic chemistry section.

Research

I work in a variety of areas which could broadly be defined as the coordination chemistry of metals and/or supramolecular materials chemistry.

As described in more detail below, my interests developed largely from early contacts with the work of Rab Mulvey (s-block metals), Ewen Smith (dyes) and the Solid-State group in Strathclyde's Pharmacy Dept. aka Alastair Florence and Norman Shankland (pharmaceutical materials).

To date this has led to over 265 publications - lately at the rate of around 25 per year.

Currently, seven people work on research projects with me (from PD, through PhD to UG levels) with recent work sponsored by AstraZeneca, Schering-Plough, the EPSRC and CCLRC and WESTChem.

s-Block Metals

Working with the Mulvey group led me to appreciate that the elegant simplicity of the fundamental properties of s-block metals could lead to beautifully complex structures of materials with intrinsic usefulness.

My highlight from this body of work was our success in changing the reactivity profiles of amide and alkyl bases by using hetero-metallic mixes of group 1 and group 2 metals (or Zn) in place of the commonly using single metal or mixed group 1 metal reagents.

Recent work describes selective metadeprotonation of toluene, tetra-deprotonation of ferrocene, ruthenocene and osmocene and mono-deprotonation of bis-benzene chromium as well as the trapping of an intermediate in the alkylation of benzophenone.

For examples see, Science, 2009, 326, 706-708; J. Amer. Chem. Soc. 2005, 127, 13106 & 2005, 127, 6184 & 2005, 127, 6920 & 2004, 126, 11612; Chem. Eur. J. 2008, 14, 8025 & 2008, 14, 65; Angew. Chem. 2007, 46, 1105 & 2005, 44, 69 & 2005, 44, 3459; Chem. Commun. 2008, 2638 & 2007, 2864 & 2006, 417 & 2006, 3208; Organometallics, 2006, 25, 2415 & 2004, 23, 1197 .

Breaking news is that Rab has even lowered himself to allowing Transition Metals into the reagents. See Angew. Chem. 2009, 48, 3317.

or see Rab’s pages if you prefer pictures -http://www.chem.strath.ac.uk/people.php?id=cbas70&page=research (external link)

Dyes and Pigments

The above work armed me with a newfound respect for all things alkaline – but also with a healthy distrust of systems that burst into flames every couple of days. Whilst looking around for a simple (and water stable) application for knowledge of s-block structures I was introduced to dyes chemistry by Prof. W. Ewen Smith. Many so called organic colourants are in fact s-block metal complexes.

We have shown that common sulphonated azo dyes have fascinating supramolecular structures ranging from solvent-seperated ion-pairs through simple chains, ladders and sheets to complex 3D networks. (See,  Chem. Eur. J. 2009, 15, 9494 & 2004, 10, 4606; Inorg. Chem. 2006, 45, 2965; Angew. Chem. 2000, 112, 652).

The hope in this type of work is always that you can correlate structure to some useful physical property, but typically not enough structural information is available to make any useful predictions.

Now there is no excuse. Modern crystallography, with fast diffractometers, synchrotron sources and structure solutions from powder diffraction data enables whole families of closely related structures to be elucidated, where previously only a few "important" compounds would be studied.

We've taken the approach of building structural databases of many related "boring" structures and gleaning information by studying patterns in the data as a whole as opposed to describing one structure at a time. (Mony a miekel maks a muckle, as my old granny would have said. Ask your local Scottish person if you want a translation.)

This has allowed us to link simple characteristics of the metals (e.g. electronegativity) or dyes (e.g. SO3position) to solid-state structural type and this in turn is linked to properties of interest to manufacturers (solubility, morphology etc).

Pharmaceutical Materials

Most recently (and in collaboration with Alastair Florence) we've started applying the mini-structural database idea that worked so well with dyes to pharmaceuticals.

They call this sort of thing salt-selection and seem to have more money than the colourants chemists, so we've upped-sticks and jumped ship. Special thanks must go here to AstraZeneca and Schering-Plough who caused this mercenary behaviour.

Its early as yet but the structures are just as interesting, the link from structure to solubility is looking strong and I feel good about looking at socially useful materials.

It would be nice to see some pretty colours again though, so any dye manufacturers with a few pounds to spare should feel free to call…

Other Activities

I am also interested in public engagement in science and give a mean talk on scientific understanding, mis-understanding and downright stupidity. Suitable for 15 to 90 year olds with or without a chemistry background.

Myself and Alastair Florence run an SCI backed course on practical crystal growth and characterisation. It is aimed at chemists and pharmacists who do not have specialist crystal growth knowledge but who need to interact with solid-state and/or formulation or salt selection specialists. Next one should be in the summer of 2010.

Finally, we (of course) offer a commercial single crystal diffraction service to industry. If you want to know more about any of the activities above then please get in touch. 

Selected Publications

Synergic sedation of sensitive anions: Alkali-mediated zincation of cyclic ethers and ethene
Kennedy AR, Klett J, Mulvey RE & Wright DS
Science, 2009, 326, 706-708.
Supramolecular structure in s-block metal complexes of sulfonated monoazo dyes: Discrepant packing and bonding behavior of ortho-sulfonated azo dyes
Kennedy AR, Andrikopoulos PC, Arlin J-B, Armstrong DR, Duxbury N, Graham DV & Kirkhouse JBA
Chem. Eur. J., 2009, 15, 9494-9504.
Structural tracking of the potassium-mediated magnesiation of anisole
Clegg W, Conway B, Garcia-Alvarez P, Kennedy AR, Mulvey RE, Russo L, Sassmannshausen J and Tuttle T
Chem. Eur. J., 2009, 15, 10702-10706.
Direct C-H metalation with chromium(II) and iron(II): Transition-metal host / benzenediide guest magnetic inverse-crown complexes
Albores P, Carrella LM, Clegg W, Garcia-Alvarez P, Kennedy AR, Klett J, Mulvey RE, Rentschler E and Russo L
Angew. Chem, 2009, 48, 3317-3321.
Amidine dications. Isolation and [Fe]-hydrogenase related hydrogenation
Corr MJ, Gibson KF, Kennedy AR & Murphy JA
J. Am. Chem. Soc., 2009, 131, 9174-9175.