The ozonation of silanes and germanes: an experimental and theoretical investigation.
Ozonation of various silanes and germanes produced the corresponding hydrotrioxides, R3SiOOOH and R3GeOOOH, which were characterized by 1H, 13C, 17O, and 29Si NMR, and by infrared spectroscopy in a two-pronged approach based on measured and calculated data. Ozone reacts with the E-H (E = Si, Ge) bond via a concerted 1,3-dipolar insertion mechanism, where, depending on the substituents and the environment (e.g., acetone-d6 solution), the H atom transfer precedes more and more E-O bond formation. The hydrotrioxides decompose in various solvents into the corresponding silanols/germanols, disiloxanes/digermoxanes, singlet oxygen (O2(1delta(g))), and dihydrogen trioxide (HOOOH), where catalytic amounts of water play an important role as is indicated by quantum chemical calculations. The formation of HOOOH as a decomposition product of organometallic hydrotrioxides in acetone-d6 represents a new and convenient method for the preparation of this simple, biochemically important polyoxide. By solvent variation, singlet oxygen (O2(1delta(g))) can be generated in high yield.
Department of Chemistry, Faculty of Chemistry and Chemical Technology, University of Ljubljana, P.O. Box 537, 1000 Ljubljana, Slovenia.
Janez
J
Cerkovnik
Tell
T
Tuttle
Elfi
E
Kraka
Nika
N
Lendero
Bozo
B
Plesnicar
Dieter
D
Cremer
D005857:Germanium / Q000737:chemistry*; D007700:Kinetics; D008958:Models, Molecular; D010126:Ozone / Q000737:chemistry*; D012821:Silanes / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D013816:Thermodynamics
D012821:Silanes; D005857:Germanium; D010126:Ozone