Abstract: Highly selective catalytic system {(RO)3VO+[(Bu)4N+]OH} for the process of linalool to geraniol + nerol isomerization within the temperature range of 413–513 K is reported. Using the Full-size image (<1 K) NMR spectroscopy, composition and reactivity of vanadium complexes formed in the catalytic system were investigated. Mononuclear vanadium complexes (RO)3−n(R′O)nVO, where RO-linalyl and R′O-geranyl/neryl ligands, n=0, 1 and 2, are active in the isomerization reaction. The reaction of the ligand {linalool/(geraniol+nerol)} exchange is very fast and reversible, the equilibrium constant of this reaction was estimated. The rate determining step of the isomerization process is the rearrangement of the coordinated to vanadium linalyl- to geranyl/neryl ligands which, probably, proceeds via reduction–oxidation mechanism. The isomerization of linalool is a reversible reaction and two isomers (geraniol and nerol) are formed by the parallel routs. The equilibrium constant of the linalool/(geraniol+nerol) as well as geraniol/nerol isomerization slightly depends on temperature. The reaction rate is of the first-order on linalool, geraniol and nerol concentrations. The kinetic scheme and mechanism of linalool to geraniol+nerol isomerization are suggested.

Cite: Semikolenov V.A. , Ilyna I.I. , Maksimovskaya R.I.
Linalool to Geraniol/Nerol Isomerization Catalyzed by (RO)3VO Complexes: Studies of Kinetics and Mechanism
Journal of Molecular Catalysis A: Chemical. 2003. V.204-205. P.201-210. DOI: 10.1016/S1381-1169(03)00299-1 WOS Scopus РИНЦ ANCAN OpenAlex

Dates:

Submitted:	Oct 1, 2002
Accepted:	Feb 2, 2003
Published online:	Jun 11, 2003
Published print:	Sep 15, 2003

Identifiers:

Web of science:	WOS:000185387900018
Scopus:	2-s2.0-18744431097
Elibrary:	13431189
Chemical Abstracts:	2003:697990
Chemical Abstracts (print):	140:59784
OpenAlex:	W1998697686

Citing:

DB	Citing
Web of science	11
Scopus	15
Elibrary	14
OpenAlex	14

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