Black plate (656,1)

656 Chapter 22 . d-Block metal chemistry: the second and third row metals

The M’MO3 compounds crystallize with perovskite struc-
tures (Figure 5.23), and exhibit ferroelectric and piezoelec-
tric properties (see Section 13.9) which lead to uses in
electrooptical and acoustic devices.
The coordination chemistry of Nb(V) and Ta(V) is well
developed and there is a close similarity in the complexes
formed by the two metals; complexes with hard donors are
favoured. Although 6-, 7- and 8-coordinate complexes are
the most common, lower coordination numbers are observed,
e.g. in ½TaðNEt2 Þ5  (trigonal bipyramidal), ½NbðNMe2 Þ5  and
½NbOCl4 
(square-based pyramidal). The Lewis acidity of
the pentahalides, especially NbF5 and TaF5 , leads to the
formation of salts such as Cs½NbF6  and K½TaF6  (octahedral
anions), K2 ½NbF7  and K2 ½TaF7  (capped trigonal prismatic
anions), Na3 ½TaF8  and Na3 ½NbF8  (square antiprismatic
anions) and ½n Bu4 N½M2 F11  (equation 22.24 and structure
22.9).
½n Bu4 N½BF4  MF5
MF5








½n Bu4 N½MF6 



½n Bu4 N½M2 F11 
" "
and a signal consisting of 17 lines with relative intensities close
to 1 : 8 : 28 : 56 :72 : 72 : 84 : 120 : 142 : 120 :84 : 72 : 72 : 56 :28 : 8 :1.
Rationalize these data. [Ans. see S. Brownstein (1973) Inorg.
Chem., vol. 12, p. 584]
2. The anion [NbOF6 ]3
has C3v symmetry. Suggest a structure
for this ion. [Ans. see Figure 19.7a; O atom in unique site]
Niobium(IV) and tantalum(IV)
With the exception of TaF4 , all halides of Nb(IV) and Ta(IV)
are known. They are dark solids, prepared by reducing the
respective MX5 by heating with metal M or Al. Niobium(IV)
fluoride is paramagnetic (d 1 ) and isostructural with SnF4
(13.12). In contrast, MCl4 , MBr4 and MI4 are diamagnetic
(or weakly paramagnetic) consistent with the pairing of
metal atoms in the solid state. The structures of NbCl4 and
NbI4 are known in detail, and consist of edge-sharing
distorted NbX6 octahedra (22.11) with alternating Nb
Nb

distances (303 and 379 pm in NbCl4 ; 331 and 436 pm in

ðM ¼ Nb; TaÞ ð22:24Þ NbI4 ).

F F –
F F

F M F M F

F F
F F
M = Nb, Ta short long short
Nb–Nb Nb–Nb Nb–Nb
(22.9)
(22.11)
Other complexes include:
The tetrahalides are readily oxidized in air (e.g. NbF4 to
. octahedral: ½NbðH2 OÞðOÞF4 
(Figure 22.5b), NbO2 F) and disproportionate on heating (reaction 22.25).
½NbðNCS-NÞ6 
, ½NbF5 ðOEt2 Þ,


mer-½NbCl3 ðOÞðNCMeÞ2 ; 2TaCl4

TaCl5 þ TaCl3
"
ð22:25Þ
. intermediate between octahedral and trigonal prismatic: Blue-black NbO2 is formed by reduction of Nb2 O5 at 1070 K
½NbðSCH2 CH2 SÞ3 
; using H2 or NH3 ; it has a rutile structure, distorted by
. pentagonal bipyramidal: ½NbðH2 OÞ2 ðOÞðoxÞ2 
(22.10); pairing of Nb atoms (Nb
Nb ¼ 280 pm).
½NbðOÞðoxÞ3 3
(oxo ligand in an axial site); A range of Nb(IV) and Ta(IV) complexes are formed by
. dodecahedral: ½NbðZ2 -O2 Þ4 3
, ½NbðZ2 -O2 Þ2 ðoxÞ2 3
; reactions of MX4 (X ¼ Cl, Br, I) with Lewis bases containing
. square antiprismatic: ½TaðZ2 -O2 Þ2 F4 3
. N-, P-, As-, O- or S-donors, or by reduction of MX5 in the
(For explanation of the Z-nomenclature, see Box 18.1.) presence of a ligand. Coordination numbers are typically 6,
7 or 8; for example, some structures confirmed for the solid
OH2 –
state are:
H2O O O
. octahedral: trans-½TaCl4 ðPEt2 Þ2 , cis-½TaCl4 ðPMe2 PhÞ2 ;
O Nb
. capped octahedral: ½TaCl4 ðPMe3 Þ3  (Figure 19.7b);
O O
O O . capped trigonal prismatic: ½NbF7 3
(equation 22.26);
O
. dodecahedral: ½NbðCNÞ8 4
;
O
. square antiprismatic: ½NbðoxÞ4 4
.
(22.10)
4NbF5 þ Nb þ 15KF

5K3 ½NbF7  "
ð22:26Þ

Self-study exercises Lower oxidation state halides

1. The solution 19 F NMR spectrum of [n Bu4 N][Ta2 F11 ] at 173 K Of the lower oxidation state compounds of Nb and Ta, we
shows three signals: a doublet of quintets (J ¼ 165 and focus on halides. The dark brown or black trihalides
23 Hz, respectively), a doublet of doublets (J ¼ 23 and 42 Hz) NbCl3 , NbBr3 , NbI3 , TaCl3 and TaBr3 are quite inert