Abstract: A detailed in situ Full-size image (<1 K) and Full-size image (<1 K) NMR spectroscopic characterization of the following families of alkylperoxo complexes of titanium is presented: Ti(η2-OOtBu)n(OiPr)4−n, where n = 1–4; binuclear complexes [(iPrO)3Ti(μ-OiPr)2Ti(OiPr)2(η2-OOtBu)] and [(η2-OOtBu)(iPrO)2Ti(μ-OiPr)2Ti(OiPr)2(η2-OOtBu)]; complexes with β-diketonato ligands: Ti(LL)2(OEt)(η2-OOtBu), Ti(LL)2(OiPr)(η2-OOtBu), Ti(LL)2(η2-OOtBu)2, Ti(LL)2(OtBu)(η1-OOtBu), where HLL = acetylacetone, dipivaloylmethane. These alkylperoxo complexes could not be isolated due to their instability and were studied in situ at low temperatures. Whereas the side-on (η2) coordination mode of tert-butylperoxo ligand is generally preferable, the end-on (η1) coordination caused by spatial hindrance from surrounding bulky ligands is found in two cases. The quantitative data on the reactivity of alkylperoxo complexes found towards sulfides and alkenes were obtained. The system TiO(acac)2/tBuOOH in C6H6 was reinvestigated using Full-size image (<1 K) and Full-size image (<1 K) NMR spectroscopy. The structure of the complex Ti(acac)2{CH3C(O)(OOtBu)COO} actually formed in this system was elucidated. Four types of titanium(IV) alkylperoxo complexes were detected in the Sharpless–Katsuki catalytic system using Full-size image (<1 K) NMR spectroscopy.

Cite: Babushkin D.E. , Talsi E.P.
Formation, Solution Structure and Reactivity of Alkylperoxo Complexes of Titanium
Journal of Molecular Catalysis A: Chemical. 2003. V.200. N1-2. P.165-175. DOI: 10.1016/S1381-1169(03)00039-6 WOS Scopus РИНЦ ANCAN OpenAlex

Dates:

Submitted:	Nov 28, 2002
Accepted:	Jan 13, 2003
Published online:	Feb 22, 2003
Published print:	Jun 2, 2003

Identifiers:

Web of science:	WOS:000183168200017
Scopus:	2-s2.0-0038179599
Elibrary:	13428692
Chemical Abstracts:	2003:364268
Chemical Abstracts (print):	139:373565
OpenAlex:	W2094290433

Citing:

DB	Citing
Web of science	5
Scopus	6
Elibrary	6
OpenAlex	5

Altmetrics: