Oxygen-oxygen bond homolysis in a novel titanium(IV) alkylperoxide complex, Cp2Ti(OOtBu)Cl.
Publication type: Journal Article
Publication date: 2002-11-14
scimago Q1
wos Q1
SJR: 5.554
CiteScore: 22.5
Impact factor: 15.6
ISSN: 00027863, 15205126
PubMed ID:
12465953
General Chemistry
Catalysis
Biochemistry
Colloid and Surface Chemistry
Abstract
Cp2TiCl2 reacts with NaOOtBu to form the new titanium peroxide complex, Cp2Ti(OOtBu)Cl (1), which has been characterized both in solution and in the solid state. This complex is surprisingly unreactive towards olefins and phosphines, as it does not directly transfer an oxygen atom. Instead, decomposition occurs via initial homolysis of the oxygen-oxygen bond, yielding a tert-butoxyl radical. Decomposition of 1 in the presence of phosphines yields either phosphine oxides (e.g., OPPh3) or phosphinites (e.g., tBuOPEt2), products that result from tBuO* + PR3. O-O bond homolysis is surprising because the Ti(IV) center is d0 and cannot be oxidized, where all previous clear examples of homolytic cleavage of metal peroxide complexes are facilitated by oxidation of the metal center.
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DiPasquale A. G., Kaminsky W., Mayer J. R. Oxygen-oxygen bond homolysis in a novel titanium(IV) alkylperoxide complex, Cp2Ti(OOtBu)Cl. // Journal of the American Chemical Society. 2002. Vol. 124. No. 49. pp. 14534-14535.
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DiPasquale A. G., Kaminsky W., Mayer J. R. Oxygen-oxygen bond homolysis in a novel titanium(IV) alkylperoxide complex, Cp2Ti(OOtBu)Cl. // Journal of the American Chemical Society. 2002. Vol. 124. No. 49. pp. 14534-14535.
Cite this
RIS
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TY - JOUR
DO - 10.1021/ja028500a
UR - https://doi.org/10.1021/ja028500a
TI - Oxygen-oxygen bond homolysis in a novel titanium(IV) alkylperoxide complex, Cp2Ti(OOtBu)Cl.
T2 - Journal of the American Chemical Society
AU - DiPasquale, Antonio G.
AU - Kaminsky, Werner
AU - Mayer, James R.
PY - 2002
DA - 2002/11/14
PB - American Chemical Society (ACS)
SP - 14534-14535
IS - 49
VL - 124
PMID - 12465953
SN - 0002-7863
SN - 1520-5126
ER -
Cite this
BibTex (up to 50 authors)
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@article{2002_DiPasquale,
author = {Antonio G. DiPasquale and Werner Kaminsky and James R. Mayer},
title = {Oxygen-oxygen bond homolysis in a novel titanium(IV) alkylperoxide complex, Cp2Ti(OOtBu)Cl.},
journal = {Journal of the American Chemical Society},
year = {2002},
volume = {124},
publisher = {American Chemical Society (ACS)},
month = {nov},
url = {https://doi.org/10.1021/ja028500a},
number = {49},
pages = {14534--14535},
doi = {10.1021/ja028500a}
}
Cite this
MLA
Copy
DiPasquale, Antonio G., et al. “Oxygen-oxygen bond homolysis in a novel titanium(IV) alkylperoxide complex, Cp2Ti(OOtBu)Cl..” Journal of the American Chemical Society, vol. 124, no. 49, Nov. 2002, pp. 14534-14535. https://doi.org/10.1021/ja028500a.