Research Interests
Our
group is interested in the chemistry of reactive intermediates.
These are compounds that are formed and destroyed in the course of a
chemical reaction, and are responsible for chemical reactivity.
Depending on the intermediate, these species have lifetimes ranging
from thousandths to billionths of a second. We, in conjunction with
our collaborators, use a number of techniques; from standard
analytical methods (UV, NMR, GC and HPLC) to highly specialized
techniques such as laser flash photolysis (LFP), matrix isolated
infra-red and EPR spectrometry, as well as high-level computational
methods, to understand the structure and reactivity of these
short-lived species.
Current Research
Projects
The
Chemistry of Heteroaryl Nitrenes
We
have found that the nitrenopyridine N-oxides
exhibit chemistry which is unlike that of simple aryl nitrenes, and
the nature of the chemistry observed depends on the position of the
nitreno- group, relative to the N-oxide
moiety. We have observed the photochemistry of these species at both
298K, and at cryogenic temperatures:
Our
current work involves investigations of the effect of substitution,
and the photochemistry of nitreno-quinoline and isoquinoline systems,
as well as di-N-oxide
systems.
- Poole, J.S. “A Computational Study of the Chemistry of Substituted 3-Nitrenopyridine 1-Oxides”, J. Mol. Struct.:THEOCHEM, 2009, 894, 93.
- Crabtree, K.N.; Hostetler, K.J.; Munsch, T.E.; Neuhaus, P.; Lahti, P.L.; Sander, W.; Poole, J.S. “Comparative Study of the Photochemistry of the Azidopyridine 1 Oxides”, J. Org. Chem., 2008, 73, 3441.
- Hostetler, K.J.; Crabtree, K.N.; Poole, J.S. "The Photochemistry of 4-Azidopyridine-1-Oxide", J. Org. Chem., 2006, 71, 9023-9029.
The
Chemistry of Hydroxyl Radical
We
are performing combined laser flash photolysis and product analysis
studies to understand the reactivity and selectivity of hydroxyl
radical reaction with aromatic substrates in non-aqueous, and
partially aqueous solvent systems. Early LFP studies indicate that
the reactions are largely dominated by hydroxyl addition reactions,
and the measured rates of reaction at 298K show correlations
indicative of charge-transfer contributions in the transition state.
Unfortunately, LFP studies are unable to elucidate the chemo- and
regioselectivity of such reactions. We have developed a product
analysis method that allows us to probe these issues, and investigate
their temperature dependence.
- DeMatteo, M; Poole, J S; Shi, X; Sachdeva, R; Hatcher, P G; Hadad, C M; Platz, M S; "On the Electrophilicity of Hydroxyl Radical: A Laser Flash Photolysis and Computational Study." J. Am. Chem. Soc. 2005, 127, 7094.
- Poole, J S; Shi, X; Hadad, C M; Platz, M S; "Reaction of Hydroxyl Radical with Aromatic Hydrocarbons in Non-Aqueous Solutions — a Laser Flash Photolysis Study in Acetonitrile." J. Phys. Chem. A. 2005, 109, 2547.