The metal

The reactivity of Ni metal resembles that of Co (e.g. equation 22.89). It is attacked by dilute
mineral acids, made passive by concentrated HNO3, and is resistant to aqueous alkalis.

The bulk metal is oxidized by air or steam only at high temperatures, but Raney nickel (see
Section 22.2) is pyrophoric Nickel reacts with F2 to give a coherent coating of NiF2 which prevents
further attack; hence the use of nickel and its alloy Monel metal (68% Ni and 32% Cu) in
apparatus for handling F2 or xenon fluorides. With Cl2, Br2 and I2, Ni(II) halides are formed. At
elevated temperatures, Ni reacts with P, S and B and a range of different phosphide (see Section
15.6), sulfide and boride (see Section 13.10) phases are known. Nickel(II) is far the most
important oxidation state for the metal (Table 20.3). Low oxidation states are most common in
organometallic species (Chapter 24), but other Ni(0) species include [Ni(PF3)4] and [Ni(CN)4]4_.
Yellow
K4[Ni(CN)4] is made by reduction of K2[Ni(CN)4] in liquid NH3 using excess K, but oxidizes
immediately on
exposure to air.

Nickel(IV) and nickel(III)

Nickel(IV) is present in only a few species, and its formation requires extremely strong oxidants,
e.g. K2[NiF6] is prepared from NiCl2, F2 and KCl. The salt [Xe2F11]2[NiF6] (Figure 18.5) is made
fromXeF2, KrF2 and NiF2. Octahedral [NiF6]2_ is diamagnetic (low-spin d 6) and the red K+ salt
crystallizes with the K2[PtF6] structure (see Mn(IV), Section 22.8). Above 620 K, K2[NiF6]
decomposes to K3[NiF6]. Salts of [NiF6]2_ are powerful oxidants, and [NF4]2[NiF6] has been used as
an oxidizing agent in some solid propellants. It decomposes on heating according to equation
22.90. Nickel(IV) fluoride can be prepared from K2[NiF6] and BF3 or AsF5, but is unstable above
208K (equation 22.91).

Nickel(IV) is present in KNiIO6, formally a salt of [IO6]5_ (see Section 17.9); it is formed by
oxidation of
[Ni(OH2)6]2+ by [S2O8]2_ in the presence of [IO4]_. The structure of KNiIO6 can be considered as an
hcp
array of O atoms with K, Ni and I occupying octahedral sites. Impure NiF3 is made by reaction
22.91. It is a black solid, and is a strong fluorinating agent, but decomposes when heated
(equation 22.92).

Reaction of NiCl2, KCl and F2 produces violet K3[NiF6]. Octahedral [NiF6]3_ is low-spin d 7 t2g 6eg 1+
and shows the expected JahnTeller distortion.

The black hydrous oxide Ni(O)OH is obtained by alkaline hypochlorite oxidation of aqueous Ni(II)
salts and has widespread use in NiCd rechargeable batteries (equation 22.5). It is a strong
oxidizing agent, liberating Cl2 from hydrochloric acid. Mixed metal oxides of Ni(IV) include BaNiO3
and SrNiO3, which are isostructural and contain chains of facesharing NiO6 octahedra.
Nickel(III) is a very good oxidizing agent, but is stabilized by _-donor ligands. Complexes include
[Ni(1,2-S2C6H4)2]_ (22.47) and [NiBr3(PEt3)2] (22.48). The latter has a magnetic moment of 1.72
_B, indicative of low-spin Ni(III); the solid compound is stable for only a few hours. Other ligands
used to stabilize Ni(III) include porphyrins and aza-macrocycles; in [Ni(22.49)], each set of three
N-donors and three O-donors is in a fac-arrangement about an octahedral Ni(III) centre.

Nickel(II)
Nickel(II) fluoride is made by fluorination of NiCl2; it is a yellow solid with a rutile structure (Figure
6.21). Both
NiF2 and its green tetrahydrate are commercially available. Anhydrous NiCl2, NiBr2 and NiI2 are
made by direct
combination of the elements; NiCl2 and NiI2 adopt a CdCl2 structure, while NiBr2 has a CdI2
structure (see Section 6.11). The chloride is a useful precursor in Ni(II) chemistry and can be
purchased as the yellow anhydrous salt or green hydrate. The hexahydrate contains the
[Ni(OH2)6]2+ ion in the solid state, but the dehydrate (obtained by partial dehydration of
NiCl2_6H2O) has a polymeric structure analogous to 22.37. Anhydrous NiBr2 is yellow and can be
crystallized as a number of hydrates.
Black NiI2 forms a green hexahydrate.

The water-insoluble, green NiO is obtained by thermal decomposition of NiCO3 or Ni(NO3)2 and
crystallizes with
the NaCl structure. Thin amorphous films of NiO exhibiting electrochromic behaviour (see Box
23.4) may be deposited by CVD (chemical vapour deposition, see Section 28.6) starting from
[Ni(acac)2]. Nickel(II) oxide is antiferromagnetic (TN 520K); its conducting properties are
discussed in Section 28.3. Nickel(II) oxide is basic, reacting with acids, e.g. reaction 22.93.

Oxidation of NiO by hypochlorite yields Ni(O)OH (see earlier). Aerial oxidation converts NiS to
Ni(S)OH, a fact
that explains why, although NiS is not precipitated in acidic solution, after exposure to air it is
insoluble in dilute acid. Addition of [OH]_ to aqueous solutions of Ni2+ precipitates green Ni(OH)2
which has a CdI2 structure; it is used in NiCd batteries (equation 22.5). Nickel(II) hydroxide is
insoluble in aqueous NaOH except at very high hydroxide concentrations, when it forms soluble
Na2[Ni(OH)4]; Ni(OH)2 is soluble in aqueous NH3 with formation of [Ni(NH3)6]2+. The pale green
basic carbonate, 2NiCO3_3Ni(OH)2_4H2O, forms when Na2CO3 is added to aqueous Ni2+ and it is
this carbonate that is usually bought commercially.
A range of coordination geometries is observed for nickel(II) complexes with coordination
numbers from 4 to
6 being common; octahedral and square planar geometries are most usual. Examples include:

Some structures are complicated by interconversions between square planar and tetrahedral, or
square planar
and octahedral coordination as we discuss later. In addition, the potential of some ligands to
bridge between metal centres may cause ambiguity. For example, alkali metal salts of [NiF 3]_,
[NiF4]2_ and [NiCl3]_ crystallize with extended structures, whereas salts of [NiCl4]2_ and [NiBr4]2_
contain discrete tetrahedral anions. The compounds KNiF3 and CsNiF3 are obtained by cooling
melts containing NiF2 and MHF2; KNiF3 has a perovskite structure (Figure 6.23) and is
antiferromagnetic, while CsNiF3 possesses chains of face-sharing NiF6 octahedra and is
ferrimagnetic. A similar chain structure is adopted by CsNiCl3. The antiferromagnetic K2NiF4
contains layers of corner-sharing octahedral NiF6 units (Figure 22.27a) separated by K+ ions.

In Section 22.10, we noted that [Co(acac)2] is tetrameric. Similarly, [Ni(acac)2] oligomerizes,

forming trimers
(Figure 22.27b) in which [acac]_ ligands are in chelating and bridging modes. Reaction of
[{Ni(acac)2}3] with
aqueous AgNO3 yields Ag[Ni(acac)3] containing the octahedral [Ni(acac)3]_ ion.

Solid, hydrated nickel(II) salts and their aqueous solutions usually contain green [Ni(OH2)6]2+, the
electronic spectrum of which was shown in Figure 21.21 with that of [Ni(NH3)6]2+. Salts of the
latter are typically blue, giving
violet solutions. In aqueous solution, [Ni(NH3)6]2+ is stable only in the presence of excess NH3
without which species such as [Ni(NH3)4(OH2)2]2+ form. The violet chloride, bromide or
perchlorate salts of [Ni(en)3]2+ are obtained as racemates, the cation being kinetically labile (see
Section 26.2). The octahedral complexes trans-[Ni(ClO4- O,O)2(NCMe)2] (22.50) and trans-
[Ni(ClO4-O)2(py)4] illustrate the ability of perchlorate ions to act as bidentate or monodentate
ligands respectively. The latter complex is discussed again later.

Magnetic moments of octahedral Ni(II) complexes are usually close to the spin-only value of 2.83
_B. In contrast, tetrahedral complexes possess magnetic moments _4 _B due to orbital
contributions (see Section 21.9), and square planar complexes such as [Ni(CN)4]2_ (equation
22.94) are diamagnetic. These differences in magnetic moments are invaluable in providing
information about the coordination geometry in a Ni(II) complex.

The red square planar complex bis(dimethylglyoximato)- nickel(II), [Ni(Hdmg)2] (Figure 22.28a),
is used for
gravimetric determination of nickel; Ni(II) is precipitated along with Pd(II) when the ligand H2dmg
in weakly ammoniacal solution is used as a reagent. The specificity for Ni2+ arises from the low
solubility of [Ni(Hdmg)2], not its high stability constant; all complexes of type [M(Hdmg)2], where
M2+ is a first row d-block metal ion, have stability constants of the same order. The low solubility
of [Ni(Hdmg)2] can be rationalized in terms of its solid state structure. Strong hydrogen bonding
links the two ligands (Figure 22.28a) and plays a role in determining a square planar structure. As
a consequence of the molecular framework being planar, molecules in the crystalline solid are
able to assemble into 1-dimensional stacks such that intermolecular Ni????Ni separations are
325pm (Figure 22.28b; but contrast [Cu(Hdmg)2] in Section 22.12). Bis(ethylmethylglyoximato)-
nickel(II) has a related structure, but the bulkier ligand forces the molecules to pack less
efficiently (Figure 22.28c). The fact that the latter complex is more soluble than [Ni(Hdmg)2]
supports a structuresolubility relationship.

For some Ni(II) complexes, there is only a small energy difference between structure types. In
Section 20.7, we
stated that both trigonal bipyramidal and square-based pyramidal [Ni(CN)5]3_ ions (equation
22.95) are present in crystals of [Cr(en)3][Ni(CN)5]_1.5H2O. In the anhydrous salt, however, the
anions are square-based pyramidal. It is impossible to give a simple interpretation of these
observations which may be attributed to a subtle balance of steric and electronic effects.
The preference between different 4- and 6-coordination geometries for a number of Ni(II) systems
is often marginal and examples are as follows.

Octahedral-planar
. [Ni(ClO4)2(py)4] exists in a blue, paramagnetic transoctahedral form and as a yellow
diamagnetic salt
containing square planar [Ni(py)4]2+ ions.
Salicylaldoxime (2-HOC6H4CHNOH) reacts with Ni(II) to give colourless crystals of the
square planar complex 22.51, but on dissolving in pyridine, a green solution of the
paramagnetic octahedral [Ni(2- OC6H4CHNOH)2(py)2] forms.

Halides of type NiL2X2 are generally planar when Ltrialkylphosphine, but tetrahedral when L is
triarylphosphine; when XBr and LPEtPh2 or P(CH2Ph)Ph2, both forms are known (scheme
22.96).
Nickel(I)
Nickel(I) complexes are rather rare, but this oxidation state is thought to be involved in the
catalytic function of
nickel-containing enzymes such as NiFe-hydrogenase (see Figure 29.17). Dark red K4[Ni2(CN)6]
can be prepared by Na amalgam reduction of K2[Ni(CN)4]. It is diamagnetic and the anion has
structure 22.52 in which the Ni(CN)3 units are mutually perpendicular. The reaction of K4[Ni2(CN)6]
with water liberates H2 and forms K2[Ni(CN)4].