Research in the Hudnall Group
Our research is concerned with the chemistry of both organic and organometallic polyfunctional ambiphilic molecules. We are a group of synthetic organometallic chemists, whose ultimate goals are to harness and utilize the cooperative effects in these molecules for the discovery of novel bonding interactions, reactivity toward small molecules and catalysis. In particular, our research is interested in the activation small molecules of industrial and biological importance (i.e., H2, N2, CH4, and CO2). Our current efforts are focused on using carbonyl-decorated carbenes which are electron deficient to stabilize reactive allotropes and radicals of phosphorus, arsenic, antimony, and boron.
Synthesis: At the heart of our research program lie the syntheses of organic and organometallic complexes. Our synthesis requires the manipulation of oxygen/moisture sensitive reagents, and therefore our preparation techniques include the use of glove boxes and Schlenk lines to carry out air-free synthesis. Ultimately we strive to develop high-yielding synthetic routes to the desired compounds.
Stabilization of Reactive Main Group Allotropes, Alloys and Radicals: We are currently investigating the potential of electron-deficient carbenes to stabilize main group elements, specifically P, As, Sb, or B, in low-coordinate and low-oxidation state bonding situations. We ultimately strive to develop novel allotropes and even alloys of these elements. Additionally, we are exploring the ability to oxidize or reduce these species to afford carbene-stabilized main group radicals. Such materials and complexes should appeal to a broad spectrum of chemists ranging from those interested in materials science, molecular recognition, storage of gases, and catalysis.
Students who carry out their research in the Hudnall group will learn a variety of synthetic and analytical techniques including the manipulation of highly sensitive compounds, multinuclear NMR spectroscopy, single-crystal X-ray diffraction, and density functional theory (DFT) analyses.
Rodrigues, R. R.; Dorsey, C. L.; Arceneaux, C. A.; Hudnall T. W.* Phosphaalkene vs. Phosphinidene: The Nature of the P–C Bond in Carbonyl-Decorated Carbene→PPh Adducts. Chem. Commun. 2014, 50, 162-164. Link to article Featured on back cover
Douglas, N.; Neef, C. J.; Rogers, R. A.; Stanley, J. A.; Armitage, J.; Martin, B.; Hudnall, T. W.; Brittain, W. J.* Reactivity of tetrahydrochromeno[2,3-b] indoles: chromic indicators of cyanide. J. Phys. Org. Chem. 2013, 26, 688-695. Link to article
Dorsey, C. L.; Squires, B. M.; Hudnall, T. W.* Isolation of a Neutral P8 Cluster via [2+2] Cycloaddition of a Diphosphene Facilitated by Carbene Activation of White Phosphorus. Angew. Chem. Int. Ed. 2013, 52, 4462–4465. With VIP distinction and inside front cover. Link to article Featured on inside front cover
Mushinski, R. M.; Squires, B. M.; Sincerbox, K. A.; Hudnall, T. W.* Amino-Acrylamido Carbenes: Modulating Carbene Reactivity via Decoration with an α,β-unsaturated Carbonyl Moiety. Organometallics 2012, 31, 4862-7870. Link to article
Park, J. S.; Karnas, E.; Ohkubo, K.; Chen, P.; Kadish, K. M.; Fukuzumi, S.; Bielawski, C. W.*; Hudnall, T. W.; Lynch, V. M.; Sessler, J. L.* Ion-Mediated Electron Transfer in a Supramolecular Donor-Acceptor Ensemble. Science 2010, 329, 1324–1326. Link to article