J. Spandl et al., Synthesis, structure, and reactions of vanadium acid esters VO(OR)(3): Transesterification and reaction,vith oxalic acid, Z ANORG A C, 626(10), 2000, pp. 2125-2132
Citations number
24
Categorie Soggetti
Inorganic & Nuclear Chemistry
Journal title
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
The reaction of tert.-Butyl Vanadate VO(O-tert.-Bu)(3) (1) with H2C2O4 in t
he primary alcohols ethanol and propanol results in the formation of (ROH)(
RO)(2)OVV-(C2O4)(VO)-O-V(OR)(2)(HOR) (with R = C2H5 2 and R = C3H7 3). Comp
ounds 2 and 3 are the first structurally characterized neutral, binuclear o
xo-oxalato-complexes with pentavalent vanadium. The two vanadium atoms are
connected by a bisbidentate oxalate group. The {VO6} coordination at each v
anadium site is completed by a terminal oxo group, an alcohol ligand and tw
o alcoxide groups. The binuclear molecules are connected to chains by hydro
gen bonding. In the case of 2 a reversible isomorphic phase transition in t
he temperature range of -90 degrees C to -130 degrees C is observed. From m
ethanolic solution the polymeric Methyl Vanadate (1)(infinity)[VO(OMe)(3)]
(4) was obtained by transesterification. A report on the crystal structures
of 1, 2 and 3 as well as a redetermination of the structure of 4 is given.
Crystal data 1, orthorhombic, Cmc2(1), a = 16.61(2) Angstrom, b = 9.274(6)
Angstrom, c = 10.784(7) Angstrom, V = 1662(2) Angstrom(3), Z = 4, d(c) = 1.
144 gcm(-1); 2 (-90 degrees C), monoclinic, I2/a, a = 33.502(4) Angstrom, b
= 7.193(1) Angstrom, c = 15.903(2) Angstrom und beta = 143.060(3)degrees,
V = 2303(1) Angstrom(3), Z = 3. d(c) = 1.425 gcm(-1); 2 (-130 degrees C), m
onoclinic, I2/a, a = 33.274(4) Angstrom, b = 7.161(1) Angstrom, c = 47.554(
5) Angstrom, beta = 142.798(2)degrees, V = 6851(1) Angstrom(3), Z = 12, d(c
) =1.438 gcm(-1); Angstrom, triklinic, P (1) over bar, a = 9.017(5) Angstro
m, b = 9.754(5) Angstrom, c = 16.359(9) Angstrom, alpha = 94.87(2)degrees,
beta = 93.34(2)degrees, gamma = 90.42(2)degrees, V = 1431(1) Angstrom(3), Z
= 2, d(c) = 1.340 gcm(-1); 4, triklinic, P (1) over bar, a = 8.443(2) Angs
trom, b = 8.545(2) Angstrom, c = 9.665(2) Angstrom, alpha = 103.202(5)degre
es, beta = 96.476(5)degrees gamma = 112.730(4)degrees, V = 610.2(2) Angstro
m(3), Z = 4, d(c) = 1.742 gcm(-1).