5+(d 0)
VCl2(OR)2 ROH
V(OR)4, cr. or liq., brn., sol. in eth.,
bz., mol.: tetrahedron 13)
: ROH
V(NR2)4
V(S2)2, patronite
(C5H5)2VCl2
393
2.28
Cl2(200 )
nc
.)
H
O3; ClO3
2)
VO
(t,
VOCl2(N3),
t
! VON + N2 + Cl2
VOHal2(OR), liq.
VOHal(OR)2, liq.
VO(OR)3, cr. (R = Me) or
m = 1.1 ë 1.2
77
33.5
68
ì
dec. 190
480
subl. >110
128
130/vac.
dec. 180
21)
M[VO2(SO4)]
M3[VO2(C2O4)2]-cis, octahedron, V=O 1.63 and 1.64,
V ì O 2.00 (cis- to °) and 2.23 (trans-)
M3[VO2F4], struct.: linear gr. [O=V=O]
M2[VO2F3], Cs3[(VO2)2F5]
M[VO2Cl2], M = K ë Cs, V=O 1.56 and 1.60, V ì Cl 2.23
DH
ì
ì
ì 21)
ì
1251
740
ì
* stab., sol. in H2O 1% (viol. soln.)
VOF3 struct.: network of [VOFF4/2] octahedra,
V=O 1.57, V ì F 1.70 (termnl.), 1.8 ë 2.3 (br.); VOHal3
(Hal = Cl ë Br) in struct. and g.: tetrahedral mols.,
20)
V=O 1.56, V ì Cl 2.12, € ClVCl 111
Cl
+
P
F2 ; Br
F3
NaOR
2+
(VO)
VN
Thiovanadates (IV), sol. in H2O,
+H+ ! VS# + S + . . .
BaVS3, struct.: linear chains of
[VS4] tetrahedra, V ì V 2.81,
conductor
38)
30 Cl3V=NCl, m.p. 132, subl., in gas: monomers
) (V=N 1.65, N ì Cl 1.60, V ì Cl 2.14, € ClVCl 113,
€ VNCl 170), 14) in struct.: dimers with 2 Cl (br.)
HalN3 Cl3V=NHal, Hal = Br, I, mol.: trig. pyr. (NHal ë ax.)
t
M2S
60 (N2)
O
O
O
O
V
)
(OH )
+
L
32)
4
O
O
V
O
O
K3[VO2(O2)2(H2O)]#, yel.
K3[VO(O2)3]; K2[V(OH)(O2)3]
M3[V(O2)4] n H2O#,
M = K (blue-viol.), NH4 (colrl.)
Mn[VOm(O2)pL7 ë m ë 2p],
M = K, NH4; L = NH3, Dipy,
C2O4, F, CO3, anion: pentag.
pyramid, V at. shifted to ° at.
over equ. plane,
V=Oax. 1.61, V ì OO 1.9,
O ì O 1.43 ë 1.50 27)
V2O5
M
Cl
+
MVF4
Br
F
Xe
F
3
Cl
! V(S2)2 + V2S3 + . . .
+
(H
H+
2;
2O
5
VCl3
VF5, cr., colrl., v. hyg., m.p. 19, b.p. 48, DH=1473,
liq. . VF‡
4 + VF6 ; struct. analogue of CrF5;
in g.: mol., trig. bipyr., V ì F 1.71 (equ.), 1.73 (ax.);
+H2O ! V2O5# + HF (vigorously); [VF4]+[SbF6]
V2S5#, powder, brn., sol. in alk., M2S,
dil. HNO3, is readily oxidised in air,
N
O
[V10O28]6
M[VO2(O2)] 0.5 H2O
M2[V2O2(O2)4(H2O)]
(NH4)4[V2O11], yel., anion:
O
C+
Cl
2O
5;
2 (1
VCl4
2;
O+
[VO3]+X ,
peroxovanadyl(V) salts,
cr., red-brn.
SO
H
Cl
V2O(SO4)4, yel., unstab.
V
22)
(NH4)4[V2O3(SO4)4]
K[VO(SO4)2], in [VO6] octahedron V=O 1.52 (termnl.),
1.82 (br.) 47)
M[VOF4], cr., yel.-grn., struct.: chains of [VF5Oax.]
octahedron, V shifted to O by 0.31 from equ. plane,
V=O 1.57, V ì F 1.79 (equ.), 2.33 (ax.) 23)
M2[VOF5]; Cs3(VO)2F9
[PyH][VOCl4]; M2[VOCl5], M = K ë Cs, NH4, grn.
V
O
22)
ì
ì
ì
ì
ì
ì
ì
ì
ì
liq. (R = Et to C5H11).
V
2
M[VF6], M=NH4, K (dec. 330), Ag, [NO], [NO2],
[Xe2F11], cr., colrl.
#
H2O
Ag[VF4(OH)2] -trans
33)
M2[V(CN)7], CN V=7
M[VO2S] H2O; Na[VOS2] 2 H2O
(NH4)3[VS4], thiovadanate, cr., viol. (soln. ë cherryred), anion: tetrahedron, V ì S 2.15
NH4VO3
4)
2S
; ROH
2.14
VOCl3, liq., d = 1.829
VOBr3, liq.
22
2
ì
120
300
b.p.
V
H
VCl(NH2)3, brn.-grn.
VCl4(NO)
V2Cl7(NO), V2Cl8(NO)5, cr., subl.
694
M2VF6, anion: octahedron, V ì F 1.61 ë 2.29 16)
M2VCl6, M = K (brn.), Rb (pink), Cs (viol.)
M[VCl5], M = [PCl4], (previously "VCl5", cr.,
brn., m.p. 260 17)), [SCl3] (cr., blk., m.p. 32)
Cl 2
S2
S2
! VF3+VF5",
in struct.: octahedra layers,
VCl4, liq., red, v. hyg., m.p.
4 20, b.p. 154, slowly dec. 20
( ! VCl3 + Cl2")
VBr4, cr., red (is formed on cooling
the gas (550 ! 78 ), dec. 23
( ! VBr3+Br2),
mol.: tetrahedron 46)
{1.92
1.69
V2O3
+
300
1412
V ì Hal
K
IC Cl+
l
DH
Hal2
VO(ClO4)3, liq.
VO(NO3)3, liq.
VO(PO4) 2 H2O, cr.*)
VO(SO3F)3 cr., red
VOF3, cr.
m.p.
t)
(N
t
VO(NH2)2, blk., !VO(NH) ! (VO)3N2 ! VON
VO(OR)2, brn. powders 13)
VF4, cr., hyg., yel.-brn.,
ClO3
SO3 (SO2Cl2)
M3[VOF5]; Cs3[V2O2F7]; Cs[VOF3] 1/2H2O
M2[VOF4]; K2[VOF4(H2O)], bl.
M2[VOCl4]; Cs3[VOCl5],
anion: chains of octahedra, V ì O 1.9 ë 2.3,
V=O 1.58 ë 1.68, V ì F 1.88 ë 2.19
K3[VO(CN)5], anion: octahedron,
V=O 1.64, V ì C 2.31 (ax.), 2.14 (equ.)
15)
M2[VO(NCS)4]
OH
t
VOX3, yel. hyg. subst
M
(
°¯
Vanadates (V) 24)
M6V10O28 n H2O, M = Na (n=18), Ca/2 (17, pascoite), Ba/2 (n=19)
cr., orange anion of 10 distort. octahedra [VO6] with common edges,
V ì O 1.68, 1.80, 1.90, V ì V 3.04 ë 3.32
K3V5O14; [R4N]3HV4O12; K5V3O10; MV3O8
M4V2O7, M = Na ( H2O), K ( 2 H2O), Ag#
MVO3, M = Na, K (m.p. 520), Cs, NH4 (dec.30), Ag#, Ba/2 ( H2O), struct.: condenced
tetrahedra, trig. bipyrs., tetrag. pyrs. or octahedra, V ì O 1.62 ë 1.97
M3[VO4]n, M = Na (m.p. 866), K ( 2 H2O), Ag#, Sr, Ba, Al ( 3 H2O, steigerite),
Sc, Ln, Bi, Fe(III) (fervanite), Cu(II) ( 3 H2O, volborthite);
struct.: isolated tetrahedra, V ì O 1.75 [isostruct. to M3(PO4)n]
Pb5[VO4]3Cl, vanadinite, yel.-red, isostruct. to apatites
K(UO2)[VO4] 1.5 H2O, carnotite
Mn[VW12O40]; K4[V2W8O31]; Mn[PVxW12 ë xO40]; M7[PV12O36]; M6[H3PV14O42],
29)
(NH4)5H3Mn3V12O40 15 H2O
[VO2]+X, X = NO3, ClO4,
Cl, cr., red, strong Ox
agent, exists at pH<1
[VO2(RCOO)]4 19)
C2O24 ( CO2)
V2O5
VOF2, cr., yel.
VOCl2 cr., grn., subl., dec. 300; 2.5 H2O
VOBr2, cr., yel., dec. 180
VOI2 2.5 H2O, cr., brn.
VOHal2, hyg., readily sol. in H2O, alc.
N2O4 ( NO)
V2O3(SO4)2 2 H2O, in struct. [VO6]
octahedra and [SO4] tetrahedra,
V ì O 1.56 (termnl.), 1.78 (br.) 47)
Ba[VO(PO4)]2 4 H2O 48)
K2[VO(P2O7)], anion: tetrag. pyramid
Sr[VO(AsO4)]2, struct.: chains of octahedra, V=O 1.63, V ì O 2.0;
48)
Na14[V18O42(CO3)] 28 H2O
(NH4)2[VO(C2O4)2] 2 H2O, cr., blue
O
H2O2
HX
MN3( N2)
V
)
H 2O
,
NH 3
° 2+
M2
H+
MO
Vanadates (IV) (vanadites),
cr., yel. or brn.
Na(VO)2(OH)5; K2V3O7 2.66 H2O
MI4VO4 (ortho-)
II
I
MII
3 VO5; M2 VO4; M2VO3 (meta-)
MI2V2O5, (pyro-), from melts.
M2V4O9 7 H2O (tetra-, hypovanadates),
cr., formed from solns.
CaV4O9 5 H2O, simplotite
H8[Mo3V3O19]; M3[Mo2V4O19H7], blue
MOH
V2
O 3+
MV
ClN3
Vanadyl (IV) salts, O=VX2 31)
VO(ClO4)2 5 H2O
VOSO4#, cr., grn., n H2O, n=1 ë 3,
5 (=[VO(H2O)5]SO4(H2O)), 6 blue,
readily sol. in H2O, alc.; 0.5 H2SO4;
n M2SO4, n = 1, 2, cr., bl.
VOSeO3, light-grn.
(VO)3(PO4)2 9 H2O
VO(HPO4) n H2O
VO(H2PO4)2, blue
46)
(VO)2P2O7
VO(C2O4) n H2O, n = 2, 4
VO(RCOO)2 39)
In salt struct.: octahedral [VOX5] ion,
V=O 1.58 ë 1.67, V ì O 2.0 ë 2.2
30)
MOH
M
O 4;
MxV2O5, M = Li ë Cs, NH4, Cu, Ag, 0<x<1,
bronzes, in struct.: at. of V(IV) and V(V), CN 5
(tetrag. pyramid), V ì O 1.53 ë 1.98 18);
M5[V15O36], M8[V19O41(OH)9], anions: clusters,
sphere and ellipse, V(V) ë V(IV) 2.94
44)
3.5 +
V2O2(OH)3,
haeggite
V
(co
)
2
(N
NH4VO3
V2O5, cr., orange, m.p. 680, dec. 700, DH ˆ 1573, sol. in H2O 0:04%, sol. in ac.
and alk., volatile with H2O vapour (. H4V2O7 g.), V2O5 (liq.) . VO+
2 + VO3
(conductor), struct.: double chains of [VO5] tetrag. pyramids, V=O 1.58,
(t,
V O 1.78 2.0 (4 bonds); n H2O, n = 1 ("HVO3", navajoite), 2 ("H4V2O7"),
28)
3 ("H3VO4") ë ébrous cr.
HX
4.66+
4.8+
V3O7 H2O; V2O4.8 n H2O,
n=0.5, 3.5, blk., corvusite
VO(OH)2#, yel., sol. in ac. and
alk., duttonite 12)
2
)
O2
5
44
K
O(
2
750
4.33+
V6O13, cr., blue-blk., dec. 650,
in struct. octahedra,
34)
V ì O 1.6 ë 2.3
V4O9; V3O7 = VIV[VV
2 O7]
O
VO2, cr., hyg., m.p. 1545, b.p. 2700, DH ˆ 720,
sol. in ac. and alk., struct.: distort. rutile type,
paramontrosite; 2/3 ¯2°, doloresite 34)
(3.5 ë 3.75)+
VnO2n ë 1
V3O5, struct. analogue of Ti3O5 42)
NH4VO3
;
OH) 2
H3
(CO
; N
; H2
)
t
(
V 2O 3
O
4+(d1)
O
References
49