SYNTHESIS, CHARACTERIZATION AND REACTIVITY OF ORGANIC BISMUTH COMPOUNDS

• Main Author: Kou, Xiaodi
• Format: Others
• Language: en
• Published: Texas Christian University 2007
• Subjects: College of Science and Engineering
• Online Access: http://etd.tcu.edu/etdfiles/available/etd-07312007-125631/

SYNTHESIS, CHARACTERIZATION AND REACTIVITY OF ORGANIC BISMUTH COMPOUNDS by Xiaodi Kou, Ph.D., 2007 Department of Chemistry Texas Christian University Advisor: Dr. Tracy A. Hanna, Associate Professor of Chemistry As an environmentally benign element, bismuth has found more and more applications in advanced materials. Our research is aimed at two aspects of bismuth oxide materials. Our goal is to provide precursors for bismuth oxide. Bismuth trioxide is an important component of many ferroelectric materials, but the development of bismuth precursors is still very limited. Another goal of our research is to synthesize homogenous model systems for the catalyst of the SOHIO process. In the SOHIO process, propene is selectively oxidized to acrolein or selectively ammoxidized to acrylonitrile. The detailed mechanism of the process remains controversial. Several molybdenum and Mo/Bi bimetallic systems have been studied, but no bismuth model has been reported before. In the second chapter, I reported the isolation and full characterization of twelve bismuth aryloxide complexes, Bi(OAr)3. The substituents steric effect and electronic effects on the synthesis were studied. Phenyl substituents were utilized to study the bismuth-arene interactions. I also synthesized complexes with allyl or benzyl substituents very close to the bismuth center. These complexes can be good model systems to study the SOHIO process. The bismuth aryloxides we synthesized can also be used as sol-gel precursors for bismuth oxide materials. In the third chapter, I reported the synthesis of bismuth aryloxide amides Bi(OAr)n(NR)3-n, using a ligand exchange method (Bi(OAr)3 + Li(NR)---Bi(OAr)n(NR)3-n). The ligand exchange method is versatile for several kinds of bismuth aryloxide as well as an antimony aryloxide. The bismuth aryloxide amides were spectroscopically characterized, and four of them were characterized by X-ray diffraction. The bismuth aryloxide amides are also good precursors for Bi2O3 materials. They are volatile, light stable and low melting, with excellent solubility and tunable thermal stability. In the fourth chapter, I reported the isolation of ten monosubstituted alkali metal calix[8]arene complexes. Preliminary results were also obtained for reactions of the mono substituted alkali metallocalix[8]arenes with several kinds of bismuth compounds.