B.S., Stanford University, 1978. M.S., Stanford University, 1979 (James P. Collman). Ph.D., California Institute of Technology, 1983 (Robert Grubbs). Postdoctoral: University of California, Los Angeles, 1983–85 (Donald J. Cram). Honors and Awards: Fannie and John Hertz Foundation Fellow, 1979–83; American Cancer Society Scholar, 1984–85. At Oregon since 1989.
Research in the Doxsee group revolves around various aspects of molecular recognition phenomena. Through the design, synthesis, and exploitation of molecules that interact with each other or with metal ions, we address a number of fundamental topics, including the phase- and shape-selective assembly of solid-state materials from molecular precursors and the development of ion-selective binding agents. Through these ongoing research efforts as well as separate projects dedicated to the development of new pedagogical materials, we seek to train students in the concepts and practice of green chemistry.
Working with Professor Hutchison, Professor Doxsee has transformed the undergraduate organic laboratory curriculum so that all students now learn the fundamentals of organic chemistry within the context of green chemistry. Development of new laboratory experiments that both teach important chemical concepts and illustrate the principles of green chemistry is an ongoing activity in the Doxsee laboratory. Our other research activities, outlined below, also implicitly and explicitly address green chemical issues by focusing on the development of selective reactions that employ safer reagents, and are effected with significantly reduced energy costs.
Phase- and Shape-Selective Assembly of Solid-State Materials
Simple organic and inorganic salts are often completely insoluble in non-polar solvents. However, solutions of complexes of salts with crown ethers in such solvents may be readily prepared. These solubilized salts undergo “metathesis” reactions with other solubilized reactants, resulting in the crystallization of solid-state materials. The unique solvation and complexation interactions presented under these crystallization conditions leads to dramatic alteration of crystal form. For example, crystallization of silver bromide from water generally affords cubic or octahedral crystals, while crystallization from nonaqueous solvents affords a solvent-dependent variety of more complex crystal forms. Further control is frequently exhibited over solid-state phase as well as crystal form. Through use of small-molecule (or ion) precursors under ambient conditions, we routinely access metastable phases. For example, whereas crystallization of calcium carbonate from water affords the thermodynamic phase (calcite); crystallization from methanol solution affords a metastable phase (vaterite). Adaptation of these procedures for the preparation of binary and ternary metal oxides (e.g., WO3, MnWO4) frequently affords new metastable phases. We are applying these crystallization approaches to problems of current technological importance, particularly in the areas of optical and electronic materials.
Ion-Selective Binding Agents
Many pharmacologically active drugs, including anti-inflammatories and antitumor agents, bear the alpha-hydroxyketone functionality. Our studies, which we hope will lead to development of ion-selective sensors and a better understanding of the chemistry of these drugs in vivo, suggest this functionality is quite effective at complexation of the biochemically ubiquitous calcium ion. We have structurally characterized phenacyl alcohol, cortisone, and hydrocortisone complexes of calcium and have quantified the details of their interaction in solution with calcium and other group 2 metal ions. Related studies with hydroxamic acids, tetracycline, and the antitumor agent adriamycin are planned. These investigations, which are primarily analytical and structural in nature, are complemented by our program of design and synthesis of efficient and selective complexation agents for calcium. The latter studies include the synthesis of colorimetric binding agents for calcium, designed to allow simple and quantitative determination of calcium levels in biological fluids.
Hauser, M. R.; Doxsee, K. M.; Hope, H. "Calcium Complexation by Corticosteroids", Inorg. Chem. 2009, 48, 10780-10788.
Succaw, G. L.; Doxsee, K. M. "Palladium-Catalyzed Synthesis of a Benzofuran: A Case Study in the Development of a Green Chemistry Laboratory Experiment", Educacion Quimica (special 20th anniversary edition topical issue on Green Chemistry) 2009, 433-440.
Doxsee, K. M. "Green Chemistry-Facility-Independent Experimentation", in Green Chemistry Education: Changing the Course of Chemistry, Anastas, P. T.; Levy, I. J.; Parent, K. E., Eds.; ACS Symposium Series, Volume 1011; American Chemical Society: Washington, DC, 147-154 (2009).
Hauser, M. R.; Zakharov, L.; Doxsee, K. M.; Li, T. "Polymorphism of a Simple Organic Amide", Crystal Growth and Design 2008, 8(12), 4428-4431.
Doxsee, K. M. "Green chemistry-Inherently safer experimentation", in Microscale Chemistry Experimentation for All Ages, Schwarz, P.; Livneh, M.; Hugerat, M., Eds.; The Academic Arab College for Education, Haifa, Israel (2005).
Succaw, G. L.; Weakley, T. J. R.; Han, F.; Doxsee, K. M. "Crystal engineering with bis(thiourea) derivatives", Crystal Growth and Design 2005, 5, 2288-2298.
Jang, M.; Weakley, T. J. R.; Doxsee, K. M. "Aqueous crystallization of manganese(II) group 6 metal oxides", Chem. Mater. 2001, 13, 519-525.
Doxsee, K. M.; Francis, P. E., Jr.; Weakley, T. J. R. "Hydration, ion pairing, and sandwich motifs in ammonium nitrate complexes of crown ethers", Tetrahedron (Symposium in Print) 2000, 56, 6683-6691.
Doxsee, K. M. "Crystallization of solid-state materials via decomplexation of soluble complexes", Chemistry of Materials 1998, 10, 2610-2618.
Hanawalt, E. M.; Doxsee, K. M.; Weakley, T. J. R. "Reactions of tungsten pentacarbonyl and mercuric chloride complexes of 1,3,4-triphenyl-1,2-dihydrophosphete"; Heteroatom Chemistry 1998, 9, 21-28.
Doxsee, K. M.; Chang, R. C.; Chen, E.; Myerson, A. S.; Huang, D. "Crystallization of solid-state materials in nonaqueous gels. I. Silver bromide"; J. Am. Chem. Soc. 1998, 120, 585-586.
Doxsee, K. M.; Wierman, H. R. "Crystallization of salts of organic acids from non-conventional solvents"; Molecular Crystals and Liquid Crystals 1998, 313, 285-292.
Doxsee, K. M.; Juliette, J. J. J.; Nieckarz, G.; Zientara, K.; "Methane elimination and the formation of titanacycles: High regioselectivity in intramolecular C-H activation reactions of titanocene complexes", J. Am. Chem. Soc. 1994, 116, 2147-2148.
Hanawalt, E. M.; Doxsee, K. M.; Shen, G. S.; Weakley, T. J. R. "Reactions of 1,3,4-triphenyl-1,2-dihydrophosphete"; Heteroatom Chemistry 1998, 9, 9-19.
Doxsee, K. M.; Saulsbery, R. L. "Phase-selective synthesis of calcium carbonate polymorphs", Materials Science of the Cell, MRS Symposium Series, Vol. 489, 161-166 (1998).
Doxsee, K. M.; Jang, M. "Room temperature phase-selective synthesis of metastable lead chromium oxides", Chemical Aspects of Electronic Ceramics Processing, MRS Symposium Series, Vol. 495, 209-214 (1998).
Doxsee, K. M.; Wood, N. P.; Hanawalt, E. M.; Weakley, T. J. R.; "Synthesis and structure of 1,2-diphosphacyclopentenes"; Heteroatom Chemistry 1996, 7, 383-389.
Doxsee, K. M.; "Eight-membered rings with two heteroatoms 1,2"; in Comprehensive Heterocyclic Chemistry, 2nd Edition, Elsevier Scientific Ltd.: Oxford, Vol. 9, Ch. 21, pp. 459-494, 1996.
Doxsee, K. M.; "Eight-membered rings with two heteroatoms 1,3"; in Comprehensive Heterocyclic Chemistry, 2nd Edition, Elsevier Scientific Ltd.: Oxford, Vol. 9, Ch. 22, pp. 495-525, 1996.
Doxsee, K. M.; "Eight-membered rings with two heteroatoms 1,4"; in Comprehensive Heterocyclic Chemistry, 2nd Edition, Elsevier Scientific Ltd.: Oxford, Vol. 9, Ch. 23, pp. 527-590, 1996.
Doxsee, K. M.; "Eight-membered rings with two heteroatoms 1,5"; in Comprehensive Heterocyclic Chemistry, 2nd Edition, Elsevier Scientific Ltd.: Oxford, Vol. 9, Ch. 24, pp. 591-650, 1996.
Doxsee, K. M.; Garner, L. C.; Juliette, J. J.; Mouser, J. K. M.; Weakley, T. J. R.; Hope, H.; "Titanocene imido complexes: Generation as reactive intermediates, isolation, and structural characterization", Tetrahedron (Symposium-in-Print on Group 4 Organometallic Chemistry) 1995, 51, 4321-4332.
Doxsee, K. M.; Hagadorn, J.; Weakley, T. J. R.; "Metal- vs. hydrogen-bonding complexation in zinc complexes of 18-crown-6", Inorg. Chem. 1994, 33, 2600-2606.
Doxsee, K. M.; Juliette, J. J. J.; Zientara, K.; Weakley, T. J. R.; "Nitrosoarene and nitrosoalkane insertion reactions of titanacyclobutenes", Inorg. Chim. Acta (topical issue on Organometallics in Organic Chemistry) 1994, 222, 305-315.
Doxsee, K. M.; Keegan, D. S.; Wierman, H. R.; Hagadorn, J.; Arimura, M.; "Complexation-mediated crystallization", Pure Appl. Chem. 1993, 65, 429-434.
Doxsee, K. M.; Ferguson, C. M.; Wash, P. A.; Saulsbery, R. L.; Hope, H.; "Calcium complexation by a-hydroxy ketones. Characterization of a calcium chloride complex of phenacyl alcohol", J. Org. Chem. 1993, 58, 7557-7561.
Doxsee, K. M.; Juliette, J. J. J.; Mouser, J. K. M.; Zientara, K.; "Carbometallation reactions of dimethyltitanocene. Formation of titanocene vinyl complexes and titanacyclobutenes", Organometallics 1993, 12, 4682-4686.
Doxsee, K. M.; Juliette, J. J. J.; Mouser, J. K. M.; "Metallacyclobutene-metalla-butadiene (vinyl carbene complex) interconversions: Ring opening of titanacyclobutenes", Organometallics 1993, 12, 4742-4744.
Doxsee, K. M.; Hanawalt, E. M.; Weakley, T. J. R.; "Synthesis of difluorophosphoranes from phosphines and mercuric fluoride", Inorg. Chem. 1992, 31, 4420-4421.
Doxsee, K. M.; Hanawalt, E. M.; Weakley, T. J. R.; "Structure of difluorotriphenylphosphorane", Acta Crystallogr. 1992, C48, 1288-1290.
Doxsee, K. M.; Farahi, J. B.; Mouser, J. K. M.; "Titanium metallacycles as intermediates in the synthesis of acyclic and heterocyclic compounds", Synlett. (Account) 1992, 13-21.
Doxsee, K. M.; Wierman, H. R.; Weakley, T. J. R.; "Unusual coordination number and geometry in a potassium 18-crown-6 complex", J. Am. Chem. Soc. 1992, 114, 5165-5171.
Doxsee, K.M.; Mouser, J.K.M.; "Titanium-mediated synthesis of conjugated dienes", Tetrahedron Lett. 1991, 32, 1687-1690.
Doxsee, K. M.; Hanawalt, E. M.; Shen, G. S.; Weakley, T. J. R.; Hope, H.; Knobler, C. B.; "Effects of HgCl2 and W(CO)5 coordination on the structure of a 1,2-dihydrophosphete (phosphacyclobutene)", Inorg. Chem. 1991, 30, 3381-3389.
Doxsee, K. M.; Farahi, J. B.; Hope, H.; "Synthesis and formal [4+2] cycloaddition reactions of vinylimido complexes of titanocene", J. Am. Chem. Soc. 1991, 113, 8889-8898.
Doxsee, K. M.; "Affinity chromatography of complexation hosts", J. Inclusion Phenomena 1991, 10, 219-223.
Doxsee, K.M.; Stevens, R.; "Complexation mediated crystallization. Crystallization of sodium acetate trihydrate needles from cyclohexane solution", J. Inclusion Phenomena 1990, 9, 327-336.
Doxsee, K.M.; "Development of an advanced synthesis laboratory course in Nobel Prize winning chemistry", J. Chem. Ed. 1990, 67, 1057-1060.
Doxsee, K.M.; Farahi, J.B.; "Synthesis and reactivity of vinylimido complexes of titanocene", J. Chem. Soc., Chem. Commun. 1990, 1542-1544.
Doxsee, K.M.; Shen, G.S.; Knobler, C. B.; "Reactivity of 1,2-dihydrophosphetes: Formation and structural characterization of a formal [4+2] cycloadduct", J. Chem. Soc., Chem. Commun. 1990, 1649-1650.
Doxsee, K.M.; Mouser, J.K.M.; "Metal-vinyl vs. metal-alkyl insertion reactions of titanacyclobutenes with nitriles", Organometallics 1990, 9, 3012-3014.
Doxsee, K.M.; Shen, G.S.; Knobler, C. B.; "Uses of metallacyclobutenes in heterocyclic synthesis. Synthesis and structure of 1,2-dihydrophosphetes", J. Am. Chem. Soc. 1989, 111, 9129-9130.
Doxsee, K.M.; "Counteranion effects on complexation of cations", J. Org. Chem. 1989, 54, 4712-4715.
Doxsee, K.M.; Farahi, J.B.; "Reductive coupling of nitriles via formal [2+2] cycloadditions to the titanium-carbon double bond", J. Am. Chem. Soc. 1988, 110, 7239-7240.