TY - JOUR
T1 - The ozonation of silanes and germanes
T2 - an experimental and theoretical investigation
AU - Cerkovnik, Janez
AU - Tuttle, Tell
AU - Kraka, Elfi
AU - Lendero, Nika
AU - Plesničar, Božo
AU - Cremer, Dieter
PY - 2006/3/29
Y1 - 2006/3/29
N2 - Ozonation of various silanes and germanes produced the corresponding hydrotrioxides, R3-SiOOOH 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(1Δ 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(1Δ g)) can be generated in high yield.
AB - Ozonation of various silanes and germanes produced the corresponding hydrotrioxides, R3-SiOOOH 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(1Δ 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(1Δ g)) can be generated in high yield.
KW - ozonation
KW - infrared spectometry
KW - decomposition
UR - http://www.scopus.com/inward/record.url?scp=84962377336&partnerID=8YFLogxK
UR - https://pubs.acs.org/journal/jacsat
U2 - 10.1021/ja058065v
DO - 10.1021/ja058065v
M3 - Article
C2 - 16551118
AN - SCOPUS:84962377336
SN - 0002-7863
VL - 128
SP - 4090
EP - 4100
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 12
ER -