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
Journal Article
·
· Inorganic Chemistry; (USA)
- 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), Journal Name: Inorganic Chemistry; (USA) Vol. 29:16; ISSN 0020-1669; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
CHEMICAL PREPARATION
CHLORINE 35
CHLORINE 37
CHLORINE COMPOUNDS
CHLORINE ISOTOPES
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DATA
DIFFRACTION
ESTERS
EXPERIMENTAL DATA
HALOGEN COMPOUNDS
INFORMATION
INTERMEDIATE MASS NUCLEI
ISOTOPES
LIGHT NUCLEI
MOLECULAR STRUCTURE
NMR SPECTRA
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
SCATTERING
SPECTRA
STABLE ISOTOPES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
VANADIUM 51
VANADIUM COMPLEXES
VANADIUM ISOTOPES
X-RAY DIFFRACTION
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
CHEMICAL PREPARATION
CHLORINE 35
CHLORINE 37
CHLORINE COMPOUNDS
CHLORINE ISOTOPES
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DATA
DIFFRACTION
ESTERS
EXPERIMENTAL DATA
HALOGEN COMPOUNDS
INFORMATION
INTERMEDIATE MASS NUCLEI
ISOTOPES
LIGHT NUCLEI
MOLECULAR STRUCTURE
NMR SPECTRA
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
SCATTERING
SPECTRA
STABLE ISOTOPES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
VANADIUM 51
VANADIUM COMPLEXES
VANADIUM ISOTOPES
X-RAY DIFFRACTION