Chromium(II) acetate hydrate, also known as chromous acetate, is the
coordination compound
A coordination complex consists of a central atom or ion, which is usually metallic and is called the ''coordination centre'', and a surrounding array of bound molecules or ions, that are in turn known as ''ligands'' or complexing agents. Many ...
with the
formula
In science, a formula is a concise way of expressing information symbolically, as in a mathematical formula or a ''chemical formula''. The informal use of the term ''formula'' in science refers to the general construct of a relationship betwee ...
Cr
2(CH
3CO
2)
4(H
2O)
2. This formula is commonly abbreviated Cr
2(OAc)
4(H
2O)
2. This red-coloured compound features a
quadruple bond
A quadruple bond is a type of chemical bond between two atoms involving eight electrons. This bond is an extension of the more familiar types double bonds and triple bonds. Stable quadruple bonds are most common among the transition metals in the m ...
. The preparation of chromous acetate once was a standard test of the synthetic skills of students due to its sensitivity to
air
The atmosphere of Earth is the layer of gases, known collectively as air, retained by Earth's gravity that surrounds the planet and forms its planetary atmosphere. The atmosphere of Earth protects life on Earth by creating pressure allowing f ...
and the dramatic colour changes that accompany its oxidation. It exists as the
dihydrate
In chemistry, a hydrate is a substance that contains water or its constituent elements. The chemical state of the water varies widely between different classes of hydrates, some of which were so labeled before their chemical structure was understo ...
and the
anhydrous
A substance is anhydrous if it contains no water. Many processes in chemistry can be impeded by the presence of water; therefore, it is important that water-free reagents and techniques are used. In practice, however, it is very difficult to achie ...
forms.
Cr
2(OAc)
4(H
2O)
2 is a reddish
diamagnetic
Diamagnetic materials are repelled by a magnetic field; an applied magnetic field creates an induced magnetic field in them in the opposite direction, causing a repulsive force. In contrast, paramagnetic and ferromagnetic materials are attracted ...
powder, although diamond-shaped tabular
crystal
A crystal or crystalline solid is a solid material whose constituents (such as atoms, molecules, or ions) are arranged in a highly ordered microscopic structure, forming a crystal lattice that extends in all directions. In addition, macros ...
s can be grown. Consistent with the fact that it is non
ion
An ion () is an atom or molecule with a net electrical charge.
The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by conve ...
ic, Cr
2(OAc)
4(H
2O)
2 exhibits poor solubility in
water
Water (chemical formula ) is an inorganic, transparent, tasteless, odorless, and nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living organisms (in which it acts as a ...
and
methanol
Methanol (also called methyl alcohol and wood spirit, amongst other names) is an organic chemical and the simplest aliphatic alcohol, with the formula C H3 O H (a methyl group linked to a hydroxyl group, often abbreviated as MeOH). It is a ...
.
Structure
The Cr
2(OAc)
4(H
2O)
2 molecule contains two atoms of
chromium
Chromium is a chemical element with the symbol Cr and atomic number 24. It is the first element in group 6. It is a steely-grey, lustrous, hard, and brittle transition metal.
Chromium metal is valued for its high corrosion resistance and hardne ...
, two
ligated molecules of water, and four
acetate
An acetate is a salt (chemistry), salt formed by the combination of acetic acid with a base (e.g. Alkali metal, alkaline, Alkaline earth metal, earthy, Transition metal, metallic, nonmetallic or radical Radical (chemistry), base). "Acetate" als ...
bridging ligand
In coordination chemistry, a bridging ligand is a ligand that connects two or more atoms, usually metal ions. The ligand may be atomic or polyatomic. Virtually all complex organic compounds can serve as bridging ligands, so the term is usually r ...
s. The coordination environment around each chromium atom consists of four
oxygen
Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as wel ...
atoms (one from each acetate ligand) in a square, one water molecule (in an axial position), and the other chromium atom (opposite the water molecule), giving each chromium centre an
octahedral geometry
In chemistry, octahedral molecular geometry, also called square bipyramidal, describes the shape of compounds with six atoms or groups of atoms or ligands symmetrically arranged around a central atom, defining the vertices of an octahedron. The oc ...
. The chromium atoms are joined by a quadruple bond, and the molecule has D
4h symmetry (ignoring the position of the hydrogen atoms). The same basic structure is adopted by
Rh2(OAc)4(H2O)2 and
Cu2(OAc)4(H2O)2, although these species do not have such short M–M contacts.
The quadruple bond between the two chromium atoms arises from the overlap of four
d-orbitals on each metal with the same orbitals on the other metal: the d
''z''2 orbitals overlap to give a
sigma bond
In chemistry, sigma bonds (σ bonds) are the strongest type of covalent chemical bond. They are formed by head-on overlapping between atomic orbitals. Sigma bonding is most simply defined for diatomic molecules using the language and tools of s ...
ing component, the d
''xz'' and d
''yz'' orbitals overlap to give two
pi bond
In chemistry, pi bonds (π bonds) are covalent chemical bonds, in each of which two lobes of an orbital on one atom overlap with two lobes of an orbital on another atom, and in which this overlap occurs laterally. Each of these atomic orbitals ...
ing components, and the d
''xy'' orbitals give a
delta bond
In chemistry, delta bonds (δ bonds) are covalent chemical bonds, where four lobes of one involved atomic orbital overlap four lobes of the other involved atomic orbital. This overlap leads to the formation of a bonding molecular orbital with tw ...
. This quadruple bond is also confirmed by the low
magnetic moment
In electromagnetism, the magnetic moment is the magnetic strength and orientation of a magnet or other object that produces a magnetic field. Examples of objects that have magnetic moments include loops of electric current (such as electromagnets ...
and short intermolecular distance between the two atoms of 236.2 ± 0.1
pm. The Cr–Cr distances are even shorter, 184 pm being the record, when the axial ligand is absent or the carboxylate is replaced with isoelectronic nitrogenous ligands.
History
Eugène-Melchior Péligot
Eugène-Melchior Péligot (24 March 1811 – 15 April 1890), also known as Eugène Péligot, was a French chemist who isolated the first sample of uranium metal in 1841.
Péligot proved that the black powder of Martin Heinrich Klaproth was not a ...
first reported a chromium(II) acetate in 1844. His material was apparently the
dimer
Dimer may refer to:
* Dimer (chemistry), a chemical structure formed from two similar sub-units
** Protein dimer, a protein quaternary structure
** d-dimer
* Dimer model, an item in statistical mechanics, based on ''domino tiling''
* Julius Dimer ...
ic Cr
2(OAc)
4(H
2O)
2. The unusual structure, as well as that of
copper(II) acetate
Copper(II) acetate, also referred to as cupric acetate, is the chemical compound with the formula Cu(OAc)2 where AcO− is acetate (). The hydrated derivative, Cu2(OAc)4(H2O)2, which contains one molecule of water for each copper atom, is availab ...
, was uncovered in 1951.
Preparation
The preparation usually begins with reduction of an aqueous solution of a Cr(III) compound using
zinc
Zinc is a chemical element with the symbol Zn and atomic number 30. Zinc is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 (IIB) of the periodi ...
. The resulting blue solution is treated with
sodium acetate
Sodium acetate, CH3COONa, also abbreviated Na O Ac, is the sodium salt of acetic acid. This colorless deliquescent salt has a wide range of uses.
Applications
Biotechnological
Sodium acetate is used as the carbon source for culturing bacteria ...
, which results in the rapid
precipitation
In meteorology, precipitation is any product of the condensation of atmospheric water vapor that falls under gravitational pull from clouds. The main forms of precipitation include drizzle, rain, sleet, snow, ice pellets, graupel and hail. ...
of chromous acetate as a bright red powder.
:2 Cr
3+ + Zn → 2 Cr
2+ + Zn
2+
:2 Cr
2+ + 4 OAc
− + 2 H
2O → Cr
2(OAc)
4(H
2O)
2
The synthesis of Cr
2(OAc)
4(H
2O)
2 has been traditionally used to test the synthetic skills and patience of inorganic laboratory students in
universities
A university () is an institution of higher (or tertiary) education and research which awards academic degrees in several academic disciplines. Universities typically offer both undergraduate and postgraduate programs. In the United States, t ...
because the accidental introduction of a small amount of air into the apparatus is readily indicated by the discoloration of the otherwise bright red product. The anhydrous form of chromium(II) acetate, and also related chromium(II) carboxylates, can be prepared from
chromocene
Chromocene is the organochromium compound with the formula r(C5H5)2 Like structurally related metallocenes, chromocene readily sublimes in a vacuum and is soluble in non-polar organic solvents. It is more formally known as bis(η5-cyclopentadieny ...
:
: 4 RCO
2H + 2 Cr(C
5H
5)
2 → Cr
2(O
2CR)
4 + 4
C5H6
This method provides anhydrous derivatives in a straightforward manner.
Because it is so easily prepared, Cr
2(OAc)
4(H
2O)
2 is a starting material for other chromium(II) compounds. Also, many analogues have been prepared using other
carboxylic acid
In organic chemistry, a carboxylic acid is an organic acid that contains a carboxyl group () attached to an R-group. The general formula of a carboxylic acid is or , with R referring to the alkyl, alkenyl, aryl, or other group. Carboxylic ...
s in place of acetate and using different bases in place of the water.
Applications
Chromium(II) acetate has few practical applications. It has been used to dehalogenate organic compounds such as α-bromoketones and
chlorohydrin
In organic chemistry a halohydrin (also a haloalcohol or β-halo alcohol) is a functional group in which a halogen and a hydroxyl are bonded to adjacent carbon atoms, which otherwise bear only hydrogen or hydrocarbyl groups (e.g. 2-chloroethan ...
s.
The reactions appear to proceed via 1e
− steps, and rearrangement products are sometimes observed.
Because the compound is a good reducing agent, it will reduce the O
2 found in air and can be used as an oxygen scrubber.
See also
*
Chromium(III) acetate
Chromium(III) acetate, commonly known as basic chromium acetate, describes a family of salts where the cation has the formula r3O(O2CCH3)6(OH2)3sup>+. The trichromium cation is encountered with a variety of anions, such as chloride and nitrate. ...
*
Chromium acetate hydroxide
Chromium acetate hydroxide is the coordination complex with the formula r2(OH)3(OAc)3sub>4. A dark violet solid, it crystallizes as the triacontatetrahydrate (34 molecules of water of crystallization). It is water soluble.
Structure
The complex ...
References
Further reading
*
External links
*http://www.molecules.org/coordcpds.html#Cr2OAc4H2O
(outdated)
*http://wwwchem.uwimona.edu.jm/courses/chromium.pdf
{{Acetates
Chromium(II) compounds
Acetates
Coordination complexes
Reducing agents
Chemical compounds containing metal–metal bonds
Chromium–oxygen compounds