 Assistant Professor of Chemistry
B.S. in Chemistry (and B.A. in Music Theory) - Virginia Tech
Ph.D. in Chemistry - Texas A&M University
Postdoctoral work - Max-Planck-Institut für Bioinorganische Chemie
Room: 6357
Phone: 608-262-7534
Email: berry@chem.wisc.edu
Position: Assistant Professor
Berry, J.F. Comments Inorg. Chem. 2009, 30, 28-66 Nippe, M.; Timmer, G.H.; Berry, J.F. Chem Commun. 2009, 4357-4359. Pap, J.S.; Snyder, S.; Piccoli, P.; Berry J.F. Inorg. Chem. 2009, 48, 9846-9852 Bain, G. A.; Berry, J. F. J. Chem. Educ. 2008, 85, 532-536. Diamagnetic Corrections and Pascal’s Constants Berry, J. F.; DeBeer George, S.; Neese, F. Phys. Chem. Chem. Phys. 2008, 10, 4361-4374. Electronic Structure and Spectroscopy of “Superoxidized” Iron Centers in Model Systems: Theoretical and Experimental Trends Nippe, M.; Victor, E.; Berry, J. F. Eur. J. Inorg. Chem. 2008, 5569-5572. Do Metal-Metal Multiply Bonded “Ligands” Have a trans Influence? Structural and Magnetic Comparisons of Heterometallic Cr Cr···Co and MoMo···Co Interactions Pap, J. S.; DeBeer George, S.; Berry, J. F. Angew. Chem. Int. Ed. 2008, 47, 10102-10105. Delocalized Metal-Metal and Metal-Ligand Multiple Bonding in a Linear Ru–Ru≡N Unit. Elongation of a Traditionally Short Ru≡N Multiple Bond Nippe, M.; Berry, J. F. J. Am. Chem. Soc. 2007, 129, 12684-12685. Introducing a Metal-Metal Multiply Bonded Unit as an “Axial Ligand” to Iron: Synthetic Design of a Linear Cr Cr···Fe Framework Berry, J. F.; Bill, E.; Bothe, E.; George, S. D.; Mienert, B.; Neese, F.; Wieghardt, K. Science, 2006, 312, 1937-1941. An Octahedral Coordination Complex of Iron(VI) Chae, D.-H.; Berry, J. F.; Jung, S.; Cotton, F. A.; Murillo, C. A.; Yao, Z. "Vibrational Excitations in Single Trimetal-Molecule Transistors" Nano Lett. 2006, 6, 165-168. Berry, J. F.; Bill, E.; Bothe, E.; Weyherm"ller, T.; Wieghardt, K. "Octahedral Non-Heme Non-Oxo Fe(IV) Species Stabilized by a Redox-Innocent N-Methylated Cyclam-Acetate Ligand" J. Am. Chem. Soc. 2005, 127, 11550-11551. Berry, J. F.; Cotton, F. A.; Lu, T.; Murillo, C. A.; Roberts, B. K.; Wang, X. "Molecular and electronic structures by design: Tuning symmetrical and unsymmetrical linear trichromium chains" J. Am. Chem. Soc. 2004, 126, 7082-7096. Berry, J. F.; Cotton, F. A.; Murillo, C. A. "A trinuclear EMAC-type molecular wire with redox-active ferrocenylacetylide 'alligator clips' attached" Organometallics 2004, 23, 2503-2506. Berry, J. F.; Cotton, F. A.; Daniels, L. M.; Murillo, C. A.; Wang, X. "Oxidation of Ni3(dpa)4Cl2 and Cu3(dpa)4Cl2: Nickel-nickel bonding interaction, but no copper-copper bonds" Inorg. Chem. 2003, 42, 2418-2427. Berry, J. F.; Cotton, F. A.; Daniels, L. M.; Murillo, C. A. "A trinickel dipyridylamido complex with metal-metal bonding interaction: Prelude to polynickel molecular wires and devices" J. Am. Chem. Soc. 2002, 124, 3212-3213.
| Research Description
Research Interests: Coordination chemistry - synthesis, structures, spectroscopy, and electronic structure of new types of transition metal complexes; isolation and characterization of highly-reactive high-oxidation state intermediate species; redox catalysis, especially of reactions involving multiple electron transfers; metal-ligand and metal-metal multiple bonding; heterobimetallic complexes.
Some of the most important - yet difficult to control - catalytic processes are those that add heteroatoms (e.g., N, O) to unfunctionalized organic molecules. These reactions often involve the intermediacy of species having metal-oxygen or metal-nitrogen multiple bonds, which are often unobservable because they are highly reactive. The Berry group’s interest is in synthesizing and characterizing such elusive intermediate species in order to elucidate their electronic structure, and thereby the electronic effects that govern their reactivity.
For example, compounds with a linear M–M=E structure are key intermediates in rhodium-catalyzed reactions that directly functionalize unreactive C–H bonds; prior to our work no M–M=E intermediates of this type have ever been isolated. We have succeeded in the low-temperature synthesis and characterization of an unprecedented new compound that has delocalized sigma and pi bonding throughout a linear Ru–Ru≡N chain. This remarkable electron delocalization causes the Ru≡N bond to be weaker and longer than in mononuclear Ru-nitrido compounds. In fact, the bond strength of the Ru–Ru≡N species, as measured by the Ru≡N stretching frequency, appears to be intermediate between mononuclear Ru(VI)-nitrido species and nitrogen atoms bound to a bulk Ru metal surface.
Other projects in our group involve the synthesis of heterometallic complexes of geometrically constrained porphyrin ligands or tripodal ligands. These complexes are designed to facilitate multi-electron transfer reactions relevant to energy conversion. Our goals are to develop new catalytic processes for important multi-electron reactions such as CO2 reduction and various oxidations.
Heterometallic Electronic Effects
Many metalloenzymes use a heterometallic active site (MA···MB) to catalyze reactions that are essential for life. We are interested in finding out how the presence of MA affects the electronic structure of MB, and, thereby, its reactivity. When both MA and MB are first row transition metals, the effects that we want to probe are complicated by spin-spin interactions. We have therefore initiated a study of linear MA–MA···MB compounds that have a strong MA–MA metal-metal bond. This renders the MA–MA group diamagnetic, and it is therefore possible to probe the electronic structure of MB by traditional spectroscopic and magnetic measurements. For example, we have found in recent work that a neighboring CrCr bonded group has a significant impact on the redox potential of an Fe(II) ion, lowering the potential for oxidation to Fe(III). Also, we have found that the spin state of a Co(II) ion strongly depends on the nature of its heterometallic neighbor. As shown below, a CrCr···Co complex is low-spin at temperatures below ~ 100 K, but the corresponding MoMo···Co species is high-spin.
Last Updated: November 5, 2008
NSF CAREER Award, 2008 – 2013 Ernst Haage Preis des Max-Planck-Institut für Bioanorganische Chemie (First recipient), 2006 Alexander von Humboldt Forschungsstipendium, MPI-Mülheim, Sept. 2004 - Aug. 2006 Association of Former Students Graduate Assistant Award for Research, Texas A&M, 2004 Celanese, Ltd. Outstanding Graduate Student Award, Texas A&M 2004 National Science Foundation Predoctoral Fellowship, Texas A&M 2001-2004 Graduate Merit Fellowship, Texas A&M 2000 - 2001
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