Mechanism and Design in Green and Organic Materials Chemistry

James Jackson

Professor

534 CEM

517-353-0504


Research webpage


Primary Research Area

Organic (Or)

Other Area(s) of Interest

Inorganic (In)

Material (Ma)

Theoretical and Computational (Th)

Research

(Research Description PDF)

Probing mechanisms and theory, from molecular interactions to process design, Jackson group efforts range from fundamental... :

  • Novel aspects of hydrogen bonding, including hydridic-to-protonic1-4
  • Computational modeling to design and interpret reaction mechanisms and structures5-8

...to eminently practical chemistry:

  • “Green” catalysts and pathways from renewables to useful “petro-” chemicals9-11
  • Alkali metal reductants “tamed” by dispersion in silica or alumina.12

More information can be found at

www2.chemistry.msu.edu/faculty/jackson/; two active areas are outlined below, where 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 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. Dihydrogen bonding projects have focused on crystal engineering; design of bond-selective infrared activated reactions; and searches for possible biological and synthesis significance.2

Fig. 1. ORTEP images of the (unpublished) neutron diffraction structure of NaBD4 • 2D2O. These orthogonal views show the close D…D contacts between three D2O molecules and one of the deuterons of the BD4 ion.

 

Green Chemistry: We seek to replace fossil petroleum with renewables as the basis for chemicals and fuels via catalytic paths starting from biomass-derived feedstocks.9-10 Target products are commodity and specialty chemicals and fuels. Reaction optimization is guided by mechanistic explorations of rates, substituent effects, isotopic labeling, and variations in media and conditions. Meanwhile, new nanocatalysts and reagents are also under development.11-12

Synergy: Our catalytic and electrocatalytic reductions of bio-derived feedstocks in water (practical) now intersect with the dihydrogen bond (fundamental) work; interfacial dihydrogen bonding of metal-bound hydride sites under water seems to strongly affect their reactivity. In turn, the quest for “biomass refinery operations” via electrocatalytic reduction of bio-based feedstocks unexpectedly found aryl ether cleavage over a simple Nickel electrode (Figure 2).9 Such serendipities and synergies between practical and fundamental; synthesis, structure and mechanism; and experiment and theory pull us back to the lab each day.

Fig. 2. Electrocatalytic hydrogenation (ECH) of methoxyphenols over a skeletal nickel cathode cleaves the aryl ether bonds and hydrogenates the product phenol.

 

Selected Publications

  1. Dihydrogen Bonding: Structures, Energetics, and Dynamics, Custelcean, R.; Jackson, J. E., Chem. Rev. 2001, 101, 1963-1980. doi: 10.1021/cr000021b
  2. Mechanistic Investigations into α -Hydroxycarbonyls Reduction by BH4, Marincean, S.; Fritz, M.; Scamp, R.; Jackson, J. E., J. Phys. Org. Chem. 2012, 25, 1186. doi: 10.1002/poc.2986
  3. Reciprocal Hydrogen Bonding–Aromaticity Relationships, Wu, J. I.; Jackson, J. E.; Schleyer, P. v. R., J. Am. Chem. Soc. 2014, 136, 13526. doi: 10.1021/ja507202f
  4. (Anti)aromaticity-Modulated Hydrogen Bonding, Kakeshpour, T.; Wu, J. I.; Jackson, J. E., J. Am. Chem. Soc. 2016, 138, 3427−3432
  5. 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. doi: 10.1021/ja053216f
  6. A New Tool To Guide Halofunctionalization Reactions: The Halenium Affinity (HalA) Scale Ashtekar, K. D.; Marzijarani, N. S.; Jaganathan A.; Holmes, D.; Jackson, J. E.; Borhan, B., J. Am. Chem. Soc. 2014, 136, 13355. doi: 10.1021/ja506889c
  7. Nucleofugality in Oxygen and Nitrogen Derived Pseudohalides in Menshutkin Reactions: The Importance of the Intrinsic Barrier, Spahlinger, G. W.; Jackson, J. E., Phys. Chem. Chem. Phys. 2014, 16, 24559. doi: 10.1039/C4CP03741C
  8. Polyatomic Molecules under Intense Femtosecond Laser Irradiation, Konar, A.; Shu, Y.; Lozovoy, V.; Jackson, J. E.; Levine, B.; Dantus, M., J. Phys. Chem. A 2014, 118, 11433. doi: 10.1021/jp505498t
  9. Electrocatalytic Upgrading of Model Lignin Monomers with Earth Abundant Metal Electrodes, Lam, C. H.; Lowe, C. B.; Li, Z.; Longe, K. N.; Rayburn, J. T.; Caldwell, M. A.; Houdek, C. E.; Maguire, J. B.; Saffron, C. M.; Miller, D. J.; Jackson, J. E., Green Chem. 2015, 17, 601.
  10. Mechanistic Investigation of Glycerol Hydrogenolysis, Kovacs, D. G.; Miller, D. J.; Jackson, J. E., Revue Roumaine de Chimie 2015, 60, 735-742.
  11. Structural and morphological evaluation of Ru-Pd bimetallic nanocrystals, Ma, X.; Lin, R.; Ofoli, R. Y. Mei, Z.; Jackson, J. E., Mater. Chem. Phys. 2016, 173, 1-6.
  12. Reductive N-O Cleavage of Weinreb Amides by Sodium in Alumina and Silica Gels, Jackson, J. E.; O’Brien, B. N.; Kedzior, S. K.; Fryz, G. R.; Jalloh, F. S.; Banisafar, A.; Caldwell, M. A.; Braun M. B.; Dunyak B. M.; Dye, J. L., Tetrahedron Lett. 2015, 56, 6227–6230.

CV

A.B., 1977, Harvard Univ.

Ph.D., 1987, Princeton Univ.

Postdoctoral Fellow, 1986-1988, Ohio State Univ.

Awards/Honors

2001 Outstanding Faculty Award Nominee Michigan State University (ASMSU)
1994 - 1995 Teacher-Scholar Award Michigan State University (College of Natural Science)
1993 Nominated for Teacher-Scholar Award Michigan State University
1988 New Faculty Award Camille and Henry Dreyfus Foundation
1986 Ph.D. Princeton University
1984 - 1985 Charlotte Elizabeth Procter Honorific Fellowship Princeton University
1981 Hugh Stott Taylor Fellowship in Chemistry Princeton University
1979 - 1981 Ph.D. Candidate University of Washington
1977 A.B. Harvard University