E. Kent Barefield
Professor and Associate Dean, College of Sciences
Office: 2-57 Boggs
B.S., Western Kentucky University, 1965; Ph.D., The Ohio State University, 1969; Post-doctoral Associate, DuPont's Central Research Department, 1969-1970
Professor Barefield's research interests involve problems in synthetic and mechanistic inorganic and organometallic chemistry. Projects are often collaborative and may involve colleagues in our department, in other units on campus, or at other institutions. Some current areas of interest are described below.
Organometallic Reaction Mechanisms. The focus is to attempt to understand the microscopic details of reactions that have significant synthetic application with the expectation that these reactions can then be used more efficiently. Sometimes entirely new chemistry is uncovered in the course of such studies. A recent attempt to obtain evidence for an olefin carbene intermediate by thermolysis of diastereoisomers A and B resulted in the elucidation of the complex series of reactions shown in the Scheme. Those species that have been isolated are shown in blue; others are postulated. X-ray structures have been done for A and D. The ruthenium analogs of A-C have been isolated and characterized.
New Chemistry of Nitrogen. An outgrowth of a collaborative effort concerned with the elucidation of the chemical mechanisms of gas generation (H2, N2O, N2, NH3 from NO2 - and organics) in nuclear waste storage tanks has been the realization that much is still unknown about the solution chemistry of nitrogen oxides and oxyanions, especially in highly basic media. Inferential evidence suggests that Al(III), which is also present in the nuclear wastes, promotes nitrosation of alcohols and amines via an Al-ONO species (transfer of NO+) and that under basic conditions subsequent reactions of the nitrosated products probably generate NO- . Since aluminum nitrite compounds are unknown, we have recently initiated efforts to characterize examples of such compounds and to better characterize the solution chemistry of NO- , which is mostly likely an intermediate in the formation of N2O, N2 and NH3.
"Kinetics and mechanism of cyclopropanation of cyclooctene by [Fe(h (5)-C5H5)(CO)(2)CH2SPh2]BF4," P. McCarten, E. K. Barefield, Organometallics, 1998, 17, 4645-4648.
"Chemical vapor desposition of boron-carbon films using organometallic reagents," J. S. Lewis, S. Vaidyaraman, W. J. Lackey, P. K. Agrawal, G. B. Freeman and E. K. Barefield, Mater. Lett., 1996, 27, 327.
"Thermal decomposition of nitrated tributyl phosphate ", Y. Hou, E. K. Barefield, D. W. Tedder, and S. I. Abdel-Khalik, Nucl. Tech, 1996, 113, 304-315.