James Jackson
Professor Office: 513 Chemistry
Phone: 517-355-9715 141 /
Websites: Research Group - Area
Awards & Honors
Genealogy/Graduates
Mechanism and Design in Green and Organic Materials Chemistry
(Research Description PDF - 786 kb)Jackson group projects (see www.cem.msu.edu/~jackson for more) range from the fundamental...
* Nature, scope, and applications of hydridic-to-protonic hydrogen bonding1,2
* Complexant design and synthesis for thermally robust alkalides and electrides4,5,6
* Approaches to organic-based magnetic materials by self-assembly
...to the eminently practical...
* "Green" catalytic pathways from renewables to useful "petro-" chemicals7,8
* Alkali metal reductants "tamed" by dispersion in silica or alumina.3
Two areas are discussed below, but the common thread is mechanistic. By understanding molecular interactions and reactions we seek rules to design materials and processes with targeted characteristics. From the post-doc to the high-school level, scientists trained in the group have gone on to excellent positions in academics, industry, or governmental research.
Hydridic-to-protonic hydrogen bonding: Our discovery and studies of this interaction, AKA dihydrogen bonding, began with a high school student studying NaBH4*2H2O (Fig. 1).1,2 Besides the novelty of hydrogen's serving as the nucleophile in a hydrogen bond, this work has uncovered reactions governed by the material's phase and local stoichiometry as well as a bona fide crystal-to-crystal solid state transformation. Ongoing projects focus on crystal engineering, especially design of "organic zeolites," open covalent crystalline networks (with potential for gas storage or catalysis applications); a search for biologically significant instances of dihydrogen bonding; and the use of dihydrogen bonded systems as potential candidates for IR-pumped bond-selective vibrationally activated reactions.
Green Chemistry: With Prof. Dennis Miller (MSU Chemical Engineering), we aim to replace fossil petroleum with renewables as the basis for chemical manufacturing. We target products whose market (and hence potential for commercial development) is defined not by their fuel value but by their functionality. So our catalytic paths upgrade bio-based feedstocks (e.g. carbohydrates, organic acids) to commodity (e.g. 1,2-propanediol) and specialty (chiral amino alcohols) building block chemicals. Mechanistic insight--basic science--is key to process design--practical engineering--so we focus on quantitative adsorption, kinetics, surface spectroscopy, spectroelectrochemical, and quantum chemical modeling studies, complemented by classical mechanistic explorations of substituent effects, isotopic labeling, and variations in catalyst, support, and solution makeup.
Synergy: Our work on catalytic hydrogenations of aqueous organic acids to alcohols (practical) is now intersecting the (fundamental) dihydrogen bond studies; interfacial dihydrogen bonding of metal-bound hydride sites under water appears to strongly affect their reactivity. In turn, electrocatalytic reduction of lactic acid to lactaldehyde, not propylene glycol (Figure 2), a basic science surprise, turned up7 in the purposeful quest for the "biomass refining technologies of the future." Such serendipities and synergies at the borders of practical and fundamental; synthesis, structure and mechanism; and experiment and theory pull us back inexorably to the lab each day. Come join us; there's always room for another partner in the search!
Selected Publications
1. Dihydrogen Bonding: Structures, Energetics, and Dynamics, Custelcean, R.; Jackson, J. E., Chem. Rev. 2001, 101, 1963-1980.2. Structural Reinvestigation of Ammonium Hypophosphite: Was Dihydrogen Bonding Observed Long Ago?, Marincean, S.; Custelcean, R.; Stein, R.; Jackson, J. E., Inorg. Chem. 2005, 44, 45-48.
3. Alkali Metals Plus Silica Gel: Powerful Reducing Agents and Convenient Hydrogen Sources, Dye, J. L., Cram, K. D., Urbin, S. A., Redko, M. Y., Jackson, J. E., Lefenfeld, M., J. Am. Chem. Soc. 2005, 127, 9338-9339.
4. Design and Synthesis of a Thermally Stable Organic Electride, Redko, M. Y.; Jackson, J. E.; Huang, R. H.; Dye, J. L., J. Am. Chem. Soc. 2005, 127, 12416-12422.
5. One-Pot Synthesis of 1,4,7,10,13,16,21,24-Octaazabicyclo[8.8.8]hexacosane?The Peraza Analogue of [2.2.2]Cryptand, Redko, M. Y.; Huang, R.; Dye, J. L.; Jackson, J. E., Synthesis 2006, 759-761.
6. Role of Cation Complexants in the Synthesis of Alkalides and Electrides, Dye, J. L.; Redko, M. Y.; Huang, R. H.; Jackson, J. E., Adv. in Inorg. Chem. 2007, 59, 205-231.
7. Mild Electrocatalytic Hydrogenation of Lactic Acid to Lactaldehyde and Propylene Glycol, Dalavoy, T. S.; Jackson, J. E.; Swain, G. M.; Miller, D. J.; Li, J.; Lipkowski, J. J. Catal. 2007, 246, 15-28.
8. Kinetics of Aqueous-Phase Hydrogenation of Organic Acids and Their Mixtures over Carbon Supported Ruthenium Catalyst, Chen, Y.; Jackson, J. E.; Miller, D. J., Ind. Eng. Chem. Res. 2007, 46, 3334-3340.
