Oxovanadium alkoxides: Structure, reactivity, and sup 51 V NMR characteristics. Crystal and molecular structures of VO(OCH sub 2 CH sub 2 Cl) sub 3 and VOCl sub 2 (THF) sub 2 H sub 2 O
- Universitaet Hamburg (West Germany)
The vanadyl esters VO(OR){sub 3} (R = Me, Et, Pr, iPr, sBu, tBu, CH{sub 2}CH{sub 2}F, CH{sub 2}CH{sub 2}Cl, CH{sub 2}CCl{sub 3}) have been prepared and their association properties in pentane investigated by {sup 51}V NMR. Limiting (low concentration) {delta}({sup 51}V) values depend on the bulk of R (highest {sup 51}V shielding for tBu). Shielding decreases with increasing concentration (more pronounced for small R groups), owing to the formation of oligomers, probably connected by {mu}-OR groups. The X-ray diffraction study of VO(OCH{sub 2}CH{sub 2}Cl){sub 3} reveals dimer association of molecules belonging to adjacent unit cells via long V-OR bonds (226.1 (2) pm), and a trigonal-bipyramidal geometry for each monomeric unit. From the reaction between VOCl{sub 3} and diols (glycol, 1,3-propanediol, 1,2-, 2,3-, 1,3-, and 1,4-butanediol), complexes are obtained that contain the {l brace}VOCl(OR){sub 2}{r brace} and {l brace}VOCl{sub 2}OR{r brace} moieties and the alcohol coordinated in the monofunctional or bifunctional (chelating and bridging) mode. The {sup 51}V NMR spectrum of VOCl{sub 2}OCH(Me)CH(Me)OH exhibits resolved {sup 51}V-{sup 35,37}Cl coupling: J({sup 51}V-{sup 35}Cl) = 100 Hz; J({sup 51}V-{sup 37}Cl) = 83 Hz. V{sup V}OCl{sub 2}(OCH{sub 2}CH{sub 2}CH{sub 2}OH) reacts with 1,4-butanediol to form V{sup IV}OCl{sub 2}(THF){sub 2}(OH{sub 2}). In the presence of COCL{sub 3}, THF undergoes ether splitting, chlorination, and coordination to vanadium to yield VOCl{sub 2}(OCH{sub 2}CH{sub 2}CH{sub 2}CH{sub 2}Cl). 35 refs., 7 figs., 7 tabs.
- OSTI ID:
- 6178798
- Journal Information:
- Inorganic Chemistry; (USA), Vol. 29:16; ISSN 0020-1669
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CHLORINE COMPOUNDS
CRYSTAL STRUCTURE
ESTERS
VANADIUM COMPLEXES
CHEMICAL PREPARATION
CHLORINE 35
CHLORINE 37
EXPERIMENTAL DATA
MOLECULAR STRUCTURE
NMR SPECTRA
VANADIUM 51
X-RAY DIFFRACTION
CHLORINE ISOTOPES
COHERENT SCATTERING
COMPLEXES
DATA
DIFFRACTION
HALOGEN COMPOUNDS
INFORMATION
INTERMEDIATE MASS NUCLEI
ISOTOPES
LIGHT NUCLEI
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
SCATTERING
SPECTRA
STABLE ISOTOPES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
VANADIUM ISOTOPES
400201* - Chemical & Physicochemical Properties
400202 - Isotope Effects
Isotope Exchange
& Isotope Separation