Octahedral sites in a hcp array of halogen atoms ( i.e. aBiI3 lattice ).

Gambar 21.8

Vanadium(III) forms a variety of octahedral complexes, e.g. mer-[(VCl3(THF)3)] and mer[VCl3(BuNC-C)3], which have magnetic moments close to the spin-only value for a d2 ion. The
[VF6]3- ion is present in simplesalts such as K3VF6, but various lattice structures are observed in
other salts. The reacrion of CsCl withVCl3 at 1000 K produces Cs3 [V2Cl9] ; [V2Cl9]3- ( 21.8 ) is
isomorphous with [Cr2Cl9]3- and consist of two face-sharing octahedral with no metal-metal
interaction. Examples of complexes with higher coordination numbers are know, e.g. [V(CN)7]4(pentagonal bipyramidal) made from VCl3 and KCN in aqueous solution and isolated as the K+
salt.
The oxide V2O3 (which, like Ti2O3, adopts the corundumlattice, see section 12.7) is made by
partial reduction of V2O5 using H2, or by heating (1300 K) V2O5 with vanadium. It is a black
solid which, on cooling, exhibits a metal-insulator transition at 155 K. The oxide is exclusively
basic, dissolving in acids to give [V( H2O)6]3+. The hydrated oxide may be precipitated by adding
alkali to green solutions of vanadium(III) salts. The [V(H2O)6]3+ ion is present in alums such as
[NH4]V(SO4)2.12H2O formed by electrolytic reduction of [NH4][VO3] in sulfuric acid.
Vanadium (II)
Green VCl2 is made from VCl3 and H2 at 770 K and is converted to blue VF2 by reaction with
HF and H2 ; VCl2 can also be obtained from VCl3 as described above, and similarly brown-red
VBr2 and violet VI2 can be produced from VBr3 and VI3, respectively. Vanadium(II) fluoride
isantiferromagnetic and crystallizes with a rutile lattice ( figure 5.21 ) ; VCl2, VBr2 and VI2 ( all
paramagnetic) possess CdI2 layer structures ( figure5.22 ). The dihalides are water soluble.
Vanadium(II) is present in aqueous solution as the violet, octahedral [V (H2O)6]2+ ion ; it can be
prepared by reduction of vanadium in higher oxidation states electrolytically or using zinc
amalgam. It is strongly reducing, being rapidly oxidized on exposure to air. Compounds such as
Tutton salts contain [V(H2O)6]2+ ; e.g. K2V(SO4)2.6H2O is made by adding K2SO4 to an aqueous
solution of VSO4 and forms violet crystals.
A Tutton salts has the general formula [MI]2MII(SO4)2.6H2O (compare with an alum, section
12.9).

Vanadium (II) oxide is a grey, metallic solid and is obtained by reduction of higher oxides at
high temperatures. It is non-stoichiometric, varying in composition from VO0.8 to VO1.3, and
posseses an NaCl ( figure 5.15 ) or defect NaCl lattice ( see section 27.2 ). Conducting properties
of the first row metal ( II ) oxides are compared in section 27.3.
Vanadium(II) complexes are relatively rare. They include [V(CN)6]4-, the K+ salts of which is
made by reducing K4[V(CN)7] with K metal in liquid NH3 ; the magnetic moment of 3.5
close to the spin-only value of 3.87

is

Octahedral [V(NCMe)6]2+ has been isolated in the

[ZnCl4]2- salts from the reaction of VCl3 with Et2Zn in MeCN. Treatment of VCl2.4H2O with
phen gives [V(phen)3]Cl2, for which

= 3.82

(300 K), consistent with octahedral d3.