Non-Redox Assisted Oxygen–Oxygen Bond Homolysis in Titanocene Alkylperoxide Complexes: [Cp2TiIV(η1-OOtBu)L]+/0, L = Cl−, OTf−, Br−, OEt2, Et3P
Publication type: Journal Article
Publication date: 2006-01-21
scimago Q2
wos Q1
SJR: 0.676
CiteScore: 5.1
Impact factor: 2.9
ISSN: 02767333, 15206041
PubMed ID:
18725968
Organic Chemistry
Inorganic Chemistry
Physical and Theoretical Chemistry
Abstract
The titanium(IV) alkylperoxide complex Cp2Ti(OOtBu)Cl (1) is formed on treatment of Cp2TiCl2 with NaOOtBu in THF at −20 °C. Treatment of 1 with AgOTf at −20 °C gives the triflate complex Cp2Ti(OOtBu)OTf (2), which is rapidly converted to the bromide Cp2Ti(OOtBu)Br (3) on addition of nBu4NBr. The X-ray crystal structures of 1 and 3 both show η1-OOtBu ligands. Complex 2 is stable only below −20 °C; 1H, 13C, and 19F NMR spectra suggest that it also contains an η1-OOtBu ligand. Removal of the chloride from 1 with [Ag(Et2O)2]BAr‘4 (Ar‘ = 3,5-(CF3)2C6H3) yields the etherate complex [Cp2Ti(OOtBu)(OEt2)]BAr‘4 (4). Again, coordination of a fourth ligand to the Ti center indicates an η1-OOtBu ligand in 4. These peroxide complexes do not directly oxidize olefins or phosphines. For instance, the cationic etherate complex 4 reacts with excess Et3P simply by displacement of the ether to form [Cp2Ti(η1-OOtBu)(Et3P)]BAr‘4 (5). Compounds 1−5 all decompose by O−O bond homolysis, based on trapping and computational studies....
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DiPasquale A. G., Hrovat D. A., Mayer J. R. Non-Redox Assisted Oxygen–Oxygen Bond Homolysis in Titanocene Alkylperoxide Complexes: [Cp2TiIV(η1-OOtBu)L]+/0, L = Cl−, OTf−, Br−, OEt2, Et3P // Organometallics. 2006. Vol. 25. No. 4. pp. 915-924.
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DiPasquale A. G., Hrovat D. A., Mayer J. R. Non-Redox Assisted Oxygen–Oxygen Bond Homolysis in Titanocene Alkylperoxide Complexes: [Cp2TiIV(η1-OOtBu)L]+/0, L = Cl−, OTf−, Br−, OEt2, Et3P // Organometallics. 2006. Vol. 25. No. 4. pp. 915-924.
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TY - JOUR
DO - 10.1021/om050818z
UR - https://doi.org/10.1021/om050818z
TI - Non-Redox Assisted Oxygen–Oxygen Bond Homolysis in Titanocene Alkylperoxide Complexes: [Cp2TiIV(η1-OOtBu)L]+/0, L = Cl−, OTf−, Br−, OEt2, Et3P
T2 - Organometallics
AU - DiPasquale, Antonio G.
AU - Hrovat, David A
AU - Mayer, James R.
PY - 2006
DA - 2006/01/21
PB - American Chemical Society (ACS)
SP - 915-924
IS - 4
VL - 25
PMID - 18725968
SN - 0276-7333
SN - 1520-6041
ER -
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@article{2006_DiPasquale,
author = {Antonio G. DiPasquale and David A Hrovat and James R. Mayer},
title = {Non-Redox Assisted Oxygen–Oxygen Bond Homolysis in Titanocene Alkylperoxide Complexes: [Cp2TiIV(η1-OOtBu)L]+/0, L = Cl−, OTf−, Br−, OEt2, Et3P},
journal = {Organometallics},
year = {2006},
volume = {25},
publisher = {American Chemical Society (ACS)},
month = {jan},
url = {https://doi.org/10.1021/om050818z},
number = {4},
pages = {915--924},
doi = {10.1021/om050818z}
}
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DiPasquale, Antonio G., et al. “Non-Redox Assisted Oxygen–Oxygen Bond Homolysis in Titanocene Alkylperoxide Complexes: [Cp2TiIV(η1-OOtBu)L]+/0, L = Cl−, OTf−, Br−, OEt2, Et3P.” Organometallics, vol. 25, no. 4, Jan. 2006, pp. 915-924. https://doi.org/10.1021/om050818z.