WSU CAS

College of Arts and Sciences

Department of Chemistry

Inorganic RSS feed

Our Faculty

Benny, Paul

Berkman, Cliff

Brozik, Jim

Clark, Aurora

Clark, Sue

Clowers, Brian

Crouch, Greg

Finnegan, Michael

Garner, Phil

Heiden, Zachariah

Hill, Herbert

Hipps, KW

Jones, Jeff

Kang, ChulHee

Lessmann, Jeremy

Li, Alex

Mazur, Ursula

McHale, Jeanne

Nash, Ken

Peterson, Kirk

Reilly, Peter

Ronald, Rob

Jonel Saludes

Satterlee, Jim

Scudiero, Louis

Wall, Nathalie

Wherland, Scot

Xian, Ming

Yoo, Choong-Shik

Divisions/Research Areas

Analytical Chemistry

Chemistry of Biological Systems

Computational Chemistry

Environmental Chemistry

Inorganic Chemistry

Materials Chemistry

Organic Chemistry

Physical Chemistry

Radiochemistry

Emeritus Faculty

Cooke, Manning

Crosby, Glenn

Hurst, Jim

Matteson, Don

Poshusta, Ron

Willett, Roger

Yount, Ralph

Many of our faculty are also members of the Materials Science and Engineering Program at WSU

Wherland, Scot

Professor

Address

Fulmer 151
Pullman, WA 99164-4630

(509) 335-3360
email: scot_wherland@wsu.edu

Scot Wherland

Education

  • Ph.D. Chemistry, California Institute of Technology

Research

Professor Wherland received his Ph.D. from the California Institute of Technology, where he worked with Harry Gray on the kinetics of metalloprotein electron transfer reactions. He then did postdoctoral work on protein-protein electron transfer reactions at the Weizmann Institute of Science. He came to WSU in 1979, after working at the Kettering Research Laboratory on reactions catalyzed by the purified components of the nitrogenase enzyme system.The common theme of research in our laboratory is the study of the kinetics of reactions of transition metal complexes, particularly electron transfer reactions. Electron transfer reactions are involved in most energy transfer processes from metalloproteins and metalloenzymes to batteries and many catalytic processes in organometallic chemistry. As such, a detailed understanding of the factors which control the rates of electron transfer reactions is central to understanding how these processes occur and how to design better electron transfer reagents. We are now extending our interests to reactions involving reactions of coordinated ligands.Projects in our laboratory typically involve three stages. First comes the synthesis and characterization of the reactants. This may be as simple as repeating a common synthesis, or it may be as complex as design of a new molecule to test a specific prediction of a mechanism or electron transfer theory. In this stage techniques used include organic synthesis of ligands, inert atmosphere methods for synthesis of transition metal complexes, infra-red, NMR, electronic spectroscopy, and electrochemistry for the characterization of the complexes. The second stage is the study of the kinetics of the reaction. We typically use two methods, stopped-flow spectroscopy and NMR line broadening. The stopped-flow technique is used to study reactions which occur in 0.001 to 10 seconds and which involve a color change. The NMR methods are used for reactions, such as electron self-exchange reactions, which have no net chemical change. We are also equipped to study the pressure dependence of the rate constants by stopped-flow, and thus we can determine the difference in volume on going from the reactants to the transition state. The kinetic measurements are most challenging for the mechanistic study of the reactions of coordinated ligands since complex rate laws and the formation of intermediates are involved. The last stage is the analysis of the data within the currently available theories, either electron transfer theory or a mechanism proposed to be compatible with the rate law and other observations.. Computing is involved in both the kinetic data analysis and the theory. Depending on the reaction studied and the interests of the student, any of the three stages can be emphasized from the more synthetic to the more theoretical.

Projects currently available include the following:

  1. The stopped-flow method can be used to study reactions between different metal ion complexes in order to test predictions of the effect of charge, size, ligand conjugation, solvent, and added electrolyte on the reactions rates. A type of reaction in this class is given below where “Co(cage)” represents a Co complex which totally encapsulates the metal ion, making it inert to substitution by other ligands. The following reaction involves a triply bonded dirhenium complex. The reaction is inhibited by ca. 750 fold if the Co(cage)+ is ion paired with BF4-.

Co(cage)+ + Re2Br4(PMe2Ph)4 → Co(cage) + Re2Br4(PMe2Ph)4+ 
wherland model 1wherland model 2

2.   The following reaction scheme demonstrates the different types of reactivity that the complex, especially the coordinated ligands, can undergo. The type of reactivity depends on the entering nucleophile. Phosphines with a pKa of greater than 5 follow the upper path, more basic phosphines follow the upper path. Triphenylphosphite replaces the acetonitrile. We are studying reactions such as this one to determine the mechanism and what controls the product. This work involves a collaboration with a research group in Vienna.wherland model 3

3. Current work on biological electron transfer reactions involves the study of the thermodynamics of the formation of the disulfide radical. This work is related to pulse radiolysis studies performed in collaboration with scientists at the Weizmann Institute.wherland model 4

Publications

  • Jin, Kun; Huang, Xiaoying; Pang, Long; Li, Jing; Appel, Aaron; Wherland, Scot, “[Cu(I)(bpp)]BF4: the first extended coordination network prepared solvothermally in an ionic liquid solvent”, Chemical Communications 2002, 2872-2873
  • S. Wherland, O. Farver, I. Pecht, “Electron Transfer in Nitrite Reductases”, ChemPhysChem, In press 2005
  • J. Coddington and S. Wherland, “Electron Self-Exchange of Re2X4(PMe2Ph)4(0/+) (X=Cl, Br) by 1H NMR Line Broadening in Methylene Chloride”, Inorg. Chem. 36, 6235-7 (1997)
  • Simanko, W., Sapunov, V. N., Schmid, R., Kirchner, K., Wherland, S., “Activation of 5-Cyclopentadienyl Ligands toward Nucleophilic Attack through h5 h3 Ring Slippage. Kinetics, Thermodynamics, and NMR Spectroscopy”, Organometallics 17, 2391-2393 (1998)
  • Simanko, W., Tesch, W., Sapunov, V. N., Mereiter, K., Schmid, R., Kirschner, K., “Kinetics and Mechanism of Nucleophilic Substitutions on Coordinated Polyenes and Polyenyls. 3. Activation of h5-Cyclopentadienyl Ligands toward Nucleophilic Attack through h5″, Organometallics 17, 5674-88 (1998)
  • Pfeiffer, J., Kirchner, K., Wherland, S., “Extensive inhibition by ion pairing in a bimolecular, outer-sphere electron transfer reaction, reduction of a cobalt clathrochelate by ferrocene in methylene chloride”, Inorganica Chimica Acta (2001), 313(1-2), 37-42
  • Coddington, John W.; Wherland, Scot; Hurst, James K., “Pressure Dependence of Peroxynitrite Reactions. Support for a Radical Mechanism”, Inorganic Chemistry (2001), 40(3), 528-532
Filed under Inorganic, Profile

Nash, Kenneth

Professor

Address

Fulmer 639B
Pullman, WA 99164-4630

(509) 335-2654
email: knash@wsu.edu

Kenneth Nash

Education

  • PhD Inorganic Chemistry, 1978
    Florida State University
  • MS Inorganic Chemistry, 1975
    Florida State University
  • BA Chemistry, 1972
    Lewis University

Research

After nearly 25 years of conducting and directing basic and applied research on actinide and fission product chemistry and chemical separations at Argonne National Laboratory (near Chicago) and at the U.S. Geological Survey (near Denver), Professor Nash joined the department in the fall of 2003. He completed his Ph.D. in Inorganic Chemistry at Florida State University in 1978, working under the supervision of Professor Greg Choppin. In the early years of his career, his research emphasized the application of separations techniques to the elucidation of actinide solution chemistry in environmental and geological systems. At that time, he did some of the earliest work characterizing actinide interactions with naturally-occurring humic and fulvic acids. For the past 17 years, his research has focused principally on chemical separations science and the basic coordination chemistry of actinides and important fission products (mainly lanthanides). Professor Nash has published extensively on the fundamental solution chemistry of actinides, solvent extraction and ion exchange, environmental chemistry, and on applications of basic science to solving real-world problems associated with the use of radioactive materials. He is active in the Nuclear Chemistry and Technology Division and in the Separations Science and Technology Subdivision of the Industrial and Engineering Chemistry Division of the American Chemical Society, Co-editor in Chief of the journal Solvent Extraction and Ion Exchange, Associate Editor of the journal Radiochimica Acta, on the Editorial Board of the journal Separation Science and Technology and coeditor of two symposium series books. Dr. Nash was a visiting scholar at the Japan Atomic Energy Research Institute at Tokai-mura in 2000, and is the 2003 recipient of the Glenn T. Seaborg Award for Actinide Separations. He has joined the faculty at WSU to bring some of this extensive practical experience to the task of helping to educate a new generation of nuclear/radiochemists and separation scientists.

As 21st century human society wrestles with the growing awareness that global warming might constitute a serious threat to the livability of planet earth, the great potential of fission-based nuclear power to reduce greenhouse gas emissions is returning to the forefront of public thought. However, nuclear power cannot contribute more significantly to solving the problem of global warming without a viable solution of the problems (real and perceived) of nuclear power – waste management, safety, efficiency and security. The long-term potential of nuclear fission for energy production becomes almost unlimited if we breed additional fuel from the predominant fertile isotopes of uranium and thorium, and more fully realize the potential value of other useful byproducts. To fulfill this potential, it is essential that we develop the knowledge necessary to protect the biosphere from the hazards associated with this technology. Central to finding solutions to these problems is gaining a more complete understanding of the chemistry of the long-lived radioactive materials that are created as byproducts of nuclear fission – actinides and fission products. Our research group focuses its efforts on developing new insights into the chemistry of f elements (actinides and lanthanides) through investigations of the fundamental solution chemistry of the metal ions. At the core of our research are studies of the kinetics and thermodynamics of the interactions of actinides and lanthanides with (man-made and naturally-occurring) chelating agents and redox active species in aqueous and organic solutions. One key feature of this chemistry that is incompletely understood is the influence of solute-solvent interactions on the progress of complex formation/dissociation and oxidation/reduction reactions of these ions. Another is the interrelationship between ligand structure, the numbers and nature of ligand donor atoms in a multidentate chelating agent, cation bonding strength, and selectivity, each important aspects of a successful separation. Biphasic reactions of the sort associated with solvent extraction reactions are particularly interesting. The process of transforming metal ions from hydrated free or complexed ions in water to the hydrophobic forms required for miscibility in organic solvents is characterized by many changes in both the local environment of the metal cation and its extended surroundings. Though our primary emphasis is on metal separations reactions, studies of this chemistry have implications beyond that of metal ion separation science. Increased understanding of the energetics of metal ions crossing phase boundaries (in particular, the hydrophilic-hydrophobic interactions that occur in every solvent extraction reaction) can provide important insights for related phenomena in the environment or in living systems. Furthermore, the chemical and nuclear properties of lanthanides and actinides provide a particularly diverse range of options for probing the chemical features of these reactions.

We emphasize the use of radioanalytical chemistry (that is, the use of radioactive materials at low concentrations) in our research program, but also have facilities and capabilities for conducting research on radioactive materials at concentrations amenable to the application of conventional analytical methods. We are most interested in exploring the rates and mechanisms of reactions occurring in the millisecond-seconds regime using stopped-flow spectrophotometry and NMR relaxation techniques, and in studying the thermochemistry of these reactions using potentiometry, electrochemistry, calorimetry, and (of course) radiochemistry.

 

Publications

  • E.O. Otu, R. Chiarizia, P.G. Rickert and K. L. Nash, “The Extraction of Americium and Strontium by P,P’-Di(2-ethylhexyl)benzene-1,2-diphosphonic Acid”, Solvent Extraction & Ion Exchange 20, 607-632 (2002)
  • K. L. Nash, C. Lavallette, M. Borkowski, R. T. Paine, X. Gan, “Thermodynamics of the Extraction of Am(III) And Eu(III) By 2,6-Bis[(di-2-ethylhexyldiphosphino)methyl]pyridine-N,P,P’-trioxide”, Inorganic Chemistry 41, 5849-5858, (2002)
  • K. L. Nash, M. P. Jensen, “Analytical-Scale Separations of the Lanthanides: A Review of Techniques and Fundamentals”, Separation Science and Technology 36, 1257-1282 (2001)
  • J. N. Mathur, M. S. Murali, K. L. Nash, “Actinide Partitioning – A Review”, Solvent Extraction & Ion Exchange 19, 357-390 (2001)
  • J. I. Friese, K. L. Nash, M. P. Jensen, J. C. Sullivan, “Interaction of Np(V) And U(VI) with Dipicolinic Acid”, Radiochimica Acta, 89, 35-41 (2001)

Inorganic Division

Inorganic chemistry at WSU encompasses radiopharmaceuticals, traditional synthesis, computational inorganic, properties of the solid state, the photochemistry of metals in the atmosphere, bioinorganic, and investigations into the behavior of the actinide and lanthanide elements. Our faculty are leaders in their fields, giving internationally invited lectures, organizing research conferences, writing books, and presenting their research in cover articles for high-impact journals. Members of the inorganic division include:

Paul Benny

Aurora Clark

Zachariah Heiden

KW Hipps

Jim Hurst

Alex Li

Ursula Mazur

Jeanne McHale

Ken Nash

Kirk Peterson

Peter Reilly

Jim Satterlee

Scot Wherland

Roger Willett

Choong-Shik Yoo

Filed under Faculty, Inorganic, Research

Heiden, Zachariah

Assistant Professor

Address

Fulmer 40
Pullman, WA 99164-4630
Ph. (509) 335-0936
email: zachariah.heiden@wsu.edu

Heiden, Zach

Education

  • Post-Doctoral Fellow, Pacific Northwest National Lab, 2011-2013
  • Post-Doctoral Fellow, University of Toronto, 2008-2011
  • Ph.D. University of Illinois at Urbana-Champaign, 2008
  • BS in Chemical Engineering with additional major in Chemistry, University of Wisconsin-Madison 2004

Research

  • Inorganic and Organometallic Chemistry
  • Using spectroscopic techniques to understand reactivity at the molecular level

Publications

  1. Heiden, Z. M.; Chen, S.; Mock, M. T.; Rousseau, R.; Dougherty, W. G.; Kassel, W. S.; Bullock, R. M. Inorg. Chem. 2013, 52, 4026-4039.
  2. Madhi, T. M.; Heiden, Z. M.; Grimme, S.; Stephan, D. W. Metal-Free Aromatic Hydrogenation: Aniline to Cyclohexyl-amine Derivatives. J. Am. Chem. Soc., 2012, 134, 4088-4091.
  3. Farrell, J. M.; Heiden, Z. M.; Stephan, D. W.   Racemization of Amines and Transfer Hydrogenation with Frustrated Lewis Pairs. Organometallics, 2011, 30, 4497-4500.
  4. Stephan, D. W.; Greenberg, S.; Graham, T. W.; Chase, P.; Hastie, J. J.; Geier, S. J.; Farrell, J. M.; Brown, C. C.;. Heiden, Z. M.; Welch, G. C.; Ullrich, M. Metal-Free Catalytic Hydrogenation of Polar Substrates by Frustrated Lewis Pairs. Inorg. Chem., 2011, 50, 12338-12348.
  5. Heiden, Z. M.; Stephan, D. W.  Metal-Free Diastereoselective Catalytic Hydrogenations of Imines Using B(C6F5)3. Chem. Commun., 2011, 5729-5731.
Filed under Inorganic, Profile

Crosby, Glenn

Professor Emeritus

Fellow of the American Chemical Society

Address

Chemistry Department
PO Box 644630
Pullman, WA 99164-4630

(509) 335-1516

Glen Crosby

Education

  • PhD Chemistry
    University of Washington, Seattle, WA
  • Postdoctoral Study
    Florida State University, Tallahassee, FL

Research

Professor Crosby received his Ph.D. in physical chemistry at the University of Washington under the late Paul C. Cross. He was a postdoctoral fellow with Michael Kasha at Florida State University and a member of the faculty at the University of New Mexico for ten years before moving to WSU in 1967. He has been a Fulbright Fellow and Humboldt Senior Scientist in West Germany, a visiting professor of physics in New Zealand, and a Yamada Foundation research speaker in Japan. He has also received numerous awards for his efforts in education.Professor Crosby was nominated for the Presidency of the American Chemical Society.The immediate goal of our research is to determine the structural and electronic factors controlling the optical, magnetic, and photophysical properties of metal complexes in solution, glasses, and crystalline solids. The ultimate goal is to arrive at a level of understanding such that new substances can be designed at the molecular level that will exhibit properties suitable for applications in device technology and solar energy storage systems.

The principal methods employed are chemical synthesis, X-ray, IR and Raman structural characterization, and electronic spectroscopy. Special techniques include luminescence measurements, both transient and steady-state, at low temperature (1.5-300K), time-resolved spectroscopy, and the application of intense magnetic fields to luminescent materials.

Students will gain experience in vacuum technology, cryogenic techniques, and a variety of spectroscopic methods, including the use of computers for data acquisition, data reduction, and molecular calculations. Experience with various types of lasers (Ar+, N2, Dye), photon counting techniques, boxcar methods, and optical fiber technology will be obtained.

A typical student project will involve synthesis of ligands and complexes, chemical and structural characterization, and the measurement of luminescence under various conditions of aggregation and temperature. Optical studies could include the measurement of the decay of emission after pulsed laser excitation, decay times as a function of magnetic field strength, and the monitoring of luminescence changes under the influence of transient heat pulses. Synthesis and analysis of potentially more useful compounds would be the ultimate goal.

Publications

  • Brozik, J. A. and Crosby, G. A., “Thermal Redistribution of Energy from an Excited 3pi-pi* Term to a Chemically Active 3 dd Level in [Rh(III)(NN)3](PF6)3 Complexes”, Chemical Physics Letters (in press)
  • Striplin, D. R. and Crosby, G. A., “Assignment of the Luminescing States of [Au(I)Rh(I)-(tBuNC)2(mu-dppm)2][PF6]2″, J. of Phys.Chem. (1995) 99 11041-11045
  • Striplin, D. R. and Crosby, G. A., “Excited State of Homo- and Heteronuclear-Bridged Bimetallic Complexes of Rhodium(I), Iridium(I), Platinum(II) and Gold(I). Triplet Manifold Splitting, State Assignments and Symmetry Correlations”, J. of Phys. Chem. (1995) 99 7977-7984
  • Halvorson, K., Crosby, G. A. and Wacholtz, W. F., ” Synthesis and Structural Determinations of Zinc(II) Complexes Containing Dithiol and N,N-Heterocyclic Ligands”, Inorganica Chimica Acta (1995) 228 81-88
  • Striplin, D. R., Brozik, J. A. and Crosby, G. A., “Assignment of the Luminescing States of [Au(I)Ir(I)(CO)Cl(mu-dppm)2][PF6]“, Chem. Phys. Lett. (1994) 231 159
Filed under Inorganic, Physical, Profile

Inorganic Ph.D.

The requirements for a Ph.D. in Inorganic Chemistry include the preliminary exam, two formal seminars, and course requirements.

Given below is a general outline of the requirements. There is considerable flexibility in the system to accommodate the wide range of interest included in Division of Inorganic Chemistry. Each student will prepare an individualized program appropriate to his or her interests and preparation before coming to WSU.

Course Requirements

Course requirements include the required Chemistry core courses as well as Chem 502 and 503. Other courses would depend on the individual’s research interests and individualized degree program.

Preliminary Exam

The preliminary exam in Inorganic Chemistry consists of a one day written exam and an oral exam. The written exam should be taken by the end of the fourth semester, the oral exam in the fifth semester, after the second summer. The preliminary exam system is made to accommodate the individualized degree programs of our students.

The written exam covers basic material, with some emphasis on the student’s area of specialization. The oral exam is based on the defense of a short research proposal on a topic approved by the members of the student’s committee.

This proposal is expected to include preliminary results from the student’s laboratory activities. This proposal is to be submitted to the committee at least two weeks before the exam. Students are encouraged to discuss their proposal with others, including their committee.

Formal Seminars

Two formal seminars are required. The first would normally be given by the end of the third year and should be on a topic not directly related to the individual’s research problems. Suggested topics for this seminar will be provided. The second seminar should be given several months before the completion of the Ph.D. degree, and would concern research results.

Proposal Outline

The proposal should be less than 10 pages, typed and double spaced not including figures. The proposal should demonstrate a thorough knowledge of the chemistry involved, and the creativity to recognize a problem and a method of solving it.

The proposal should be divided into the following sections:

  1. Objectives and Hypotheses: This section should be a statement of the research objectives to be achieved, the hypotheses to be tested, or the questions to be answered. Cite and evaluate related work that provides useful information.
  2. Procedure: Give enough detail to indicate the logic of the suggested approach, and show that your approach is adequate to achieve the objectives.
  3. Justification: Summarize why this work should be undertaken, in terms of its impact on current knowledge in chemistry and in the broader context of science in general.
  4. Preliminary Results
Department of Chemistry, Fulmer 305, Pullman, WA 99164-4630, 509-335-5585, Contact Us
© 2014 Washington State University | Accessibility | Policies | Copyright | Log in