Tris(ethylenediamine)cobalt(III) chloride

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Tris(ethylenediamine)cobalt(III) chloride
Tris(ethylenediamine)cobalt(III) (molecular diagram).svg
Lambda-Tris(ethylenediamine)cobalt(III)-chloride-3D-balls-by-AHRLS-2012.png
Delta-Tris(ethylenediamine)cobalt(III)-chloride-3D-balls-by-AHRLS-2012.png
Names
IUPAC name
cobalt tris(ethylenediamine) chloride
Other names
tris(ethylenediamine)cobalt(III) chloride
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
  • InChI=1S/3C2H8N2.3ClH.Co/c3*3-1-2-4;;;;/h3*1-4H2;3*1H;/q;;;;;;+3/p-3
    Key: NFUAZJFARNNNFB-UHFFFAOYSA-K
  • dihydrate::InChI=1S/3C2H8N2.3ClH.Co.2H2O/c3*3-1-2-4;;;;;;/h3*1-4H2;3*1H;;2*1H2/q;;;;;;+3;;/p-3
    Key: ALLUKJGRPOLBEF-UHFFFAOYSA-K
  • trihydrate::InChI=1S/3C2H8N2.3ClH.Co.3H2O/c3*3-1-2-4;;;;;;;/h3*1-4H2;3*1H;;3*1H2/q;;;;;;+3;;;/p-3
    Key: WBMVTRUQSMZIKW-UHFFFAOYSA-K
  • C(CN)N.C(CN)N.C(CN)N.[Cl-].[Cl-].[Cl-].[Co+3]
  • dihydrate::C(CN)N.C(CN)N.C(CN)N.O.O.Cl[Co](Cl)Cl
  • trihydrate::C(CN)N.C(CN)N.C(CN)N.O.O.O.[Cl-].[Cl-].[Cl-].[Co+3]
Properties
C6H24N6Cl3Co
Molar mass 345.59
Appearanceyellow-orange solid
Melting point 275 °C (527 °F; 548 K) (decomposes)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Tris(ethylenediamine)cobalt(III) chloride is an inorganic compound with the formula [Co(en)3]Cl3 (where "en" is the abbreviation for ethylenediamine). It is the chloride salt of the coordination complex [Co(en)3]3+. This trication was important in the history of coordination chemistry because of its stability and its stereochemistry. Many different salts have been described. The complex was first described by Alfred Werner who isolated this salt as yellow-gold needle-like crystals. [1]

Contents

Synthesis and structure

The compound is prepared from an aqueous solution of ethylenediamine and virtually any cobalt(II) salt, such as cobalt(II) chloride. The solution is purged with air to oxidize the cobalt(II)-ethylenediamine complexes to cobalt(III). The reaction proceeds in 95% yield, and the trication can be isolated with a variety of anions. A detailed product analysis of a large-scale synthesis revealed that one minor by-product was [Co(en)2Cl(H2NCH2CH2NH3)]Cl3, which contains a rare monodentate ethylenediamine ligand (protonated). [2]

The cation [Co(en)3]3+ is octahedral with Co-N distances in the range 1.947–1.981 Å. The N-Co-N angles are 85° within the chelate rings and 90° between nitrogen atoms on adjacent rings. [3]

Stereochemistry

Structure of the D-(lel)3 (or D-(lll)) isomer of [Co(en)3] . One of the three C2 symmetry axes is shown in red. Coen3lel3.svg
Structure of the Δ-(lel)3 (or Δ-(λλλ)) isomer of [Co(en)3] . One of the three C2 symmetry axes is shown in red.

The point group of this complex is D3. The complex can be resolved into enantiomers that are described as Δ and Λ. Usually the resolution entails use of tartrate salts. [4] The optical resolution is a standard component of inorganic synthesis courses. [5] Because of its nonplanarity, the MN2C2 rings can adopt either of two conformations, which are described by the symbols λ and δ. The registry between these ring conformations and the absolute configuration of the metal centers is described by the nomenclature lel (when the en backbone lies parallel with the C3 symmetry axis) or ob (when the en backbone is obverse to this same C3 axis). Thus, the following diastereomeric conformations can be identified: Δ-(lel)3, Δ-(lel)2(ob), Δ-(lel)(ob)2, and Δ-(ob)3. The mirror images of these species of course exist also. [6]

Hydrates

Cationic coordination complexes of ammonia and alkyl amines typically crystallize with water in the lattice, and the stoichiometry can depend on the conditions of crystallization and, in the cases of chiral complexes, the optical purity of the cation. Racemic [Co(en)3]Cl3 is most often obtained as the di- or trihydrate. For the optically pure salt (+)-[Co(en)3]Cl3·1.5H2O, (+)-[Co(en)3]Cl3·0.5NaCl·3H2O, and (+)-[Co(en)3]Cl3·H2O are also known. [3]

Related Research Articles

<span class="mw-page-title-main">Coordination complex</span> Molecule or ion containing ligands datively bonded to a central metallic atom

A coordination complex is a chemical compound consisting 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 metal-containing compounds, especially those that include transition metals, are coordination complexes.

<span class="mw-page-title-main">Ligand</span> Ion or molecule that binds to a central metal atom to form a coordination complex

In coordination chemistry, a ligand is an ion or molecule with a functional group that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's electron pairs, often through Lewis bases. The nature of metal–ligand bonding can range from covalent to ionic. Furthermore, the metal–ligand bond order can range from one to three. Ligands are viewed as Lewis bases, although rare cases are known to involve Lewis acidic "ligands".

Iron(III) chloride describes the inorganic compounds with the formula FeCl3(H2O)x. Also called ferric chloride, these compounds are some of the most important and commonplace compounds of iron. They are available both in anhydrous and in hydrated forms which are both hygroscopic. They feature iron in its +3 oxidation state. The anhydrous derivative is a Lewis acid, while all forms are mild oxidizing agents. It is used as a water cleaner and as an etchant for metals.

<span class="mw-page-title-main">Alfred Werner</span> Swiss chemist (1866–1919)

Alfred Werner was a Swiss chemist who was a student at ETH Zurich and a professor at the University of Zurich. He won the Nobel Prize in Chemistry in 1913 for proposing the octahedral configuration of transition metal complexes. Werner developed the basis for modern coordination chemistry. He was the first inorganic chemist to win the Nobel Prize, and the only one prior to 1973.

<span class="mw-page-title-main">Europium(III) chloride</span> Chemical compound

Europium(III) chloride is an inorganic compound with the formula EuCl3. The anhydrous compound is a yellow solid. Being hygroscopic it rapidly absorbs water to form a white crystalline hexahydrate, EuCl3·6H2O, which is colourless. The compound is used in research.

<span class="mw-page-title-main">Rhodium(III) chloride</span> Chemical compound

Rhodium(III) chloride refers to inorganic compounds with the formula RhCl3(H2O)n, where n varies from 0 to 3. These are diamagnetic solids featuring octahedral Rh(III) centres. Depending on the value of n, the material is either a dense brown solid or a soluble reddish salt. The soluble trihydrated (n = 3) salt is widely used to prepare compounds used in homogeneous catalysis, notably for the industrial production of acetic acid and hydroformylation.

<span class="mw-page-title-main">Octahedral molecular geometry</span> Molecular 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 octahedron has eight faces, hence the prefix octa. The octahedron is one of the Platonic solids, although octahedral molecules typically have an atom in their centre and no bonds between the ligand atoms. A perfect octahedron belongs to the point group Oh. Examples of octahedral compounds are sulfur hexafluoride SF6 and molybdenum hexacarbonyl Mo(CO)6. The term "octahedral" is used somewhat loosely by chemists, focusing on the geometry of the bonds to the central atom and not considering differences among the ligands themselves. For example, [Co(NH3)6]3+, which is not octahedral in the mathematical sense due to the orientation of the N−H bonds, is referred to as octahedral.

<span class="mw-page-title-main">Metal ammine complex</span>

In coordination chemistry, metal ammine complexes are metal complexes containing at least one ammonia ligand. "Ammine" is spelled this way for historical reasons; in contrast, alkyl or aryl bearing ligands are spelt with a single "m". Almost all metal ions bind ammonia as a ligand, but the most prevalent examples of ammine complexes are for Cr(III), Co(III), Ni(II), Cu(II) as well as several platinum group metals.

<span class="mw-page-title-main">Scandium chloride</span> Chemical compound

Scandium(III) chloride is the inorganic compound with the formula ScCl3. It is a white, high-melting ionic compound, which is deliquescent and highly water-soluble. This salt is mainly of interest in the research laboratory. Both the anhydrous form and hexahydrate (ScCl3•6H2O) are commercially available.

Titanium(III) chloride is the inorganic compound with the formula TiCl3. At least four distinct species have this formula; additionally hydrated derivatives are known. TiCl3 is one of the most common halides of titanium and is an important catalyst for the manufacture of polyolefins.

<span class="mw-page-title-main">Hexaamminecobalt(III) chloride</span> Chemical compound

Hexaamminecobalt(III) chloride is the chemical compound with the formula [Co(NH3)6]Cl3. It is the chloride salt of the coordination complex [Co(NH3)6]3+, which is considered an archetypal "Werner complex", named after the pioneer of coordination chemistry, Alfred Werner. The cation itself is a metal ammine complex with six ammonia ligands attached to the cobalt(III) ion.

<span class="mw-page-title-main">Dichlorobis(ethylenediamine)nickel(II)</span> Chemical compound

Dichlorobis(ethylenediamine)nickel(II) is the inorganic compound with the formula NiCl2(en)2, where en = ethylenediamine. The formula is deceptive: the compound is the chloride salt of the coordination complex [Ni2Cl2(en)4]2+. This blue solid is soluble in water and some polar organic solvents. It is prepared by ligand redistribution from [Ni(en)3]Cl2 · 2 H2O and hydrated nickel chloride:

<i>cis</i>-Dichlorobis(ethylenediamine)cobalt(III) chloride Chemical compound

cis-Dichlorobis(ethylenediamine)cobalt(III) chloride is a salt with the formula [CoCl2(en)2]Cl (en = ethylenediamine). The salt consists of a cationic coordination complex and a chloride anion. It is a violet diamagnetic solid that is soluble in water. One chloride ion in this salt readily undergoes ion exchange, but the two other chlorides are less reactive, being bound to the metal center.

<span class="mw-page-title-main">Chloropentamminecobalt chloride</span> Cobalt compound

Chloropentamminecobalt chloride is the dichloride salt of the coordination complex [Co(NH3)5Cl]2+. It is a red-violet, diamagnetic, water-soluble salt. The compound has been of academic and historical interest.

<i>trans</i>-Dichlorobis(ethylenediamine)cobalt(III) chloride Chemical compound

trans-Dichlorobis(ethylenediamine)cobalt(III) chloride is a salt with the formula [CoCl2(en)2]Cl (en = ethylenediamine). It is a green diamagnetic solid that is soluble in water. It is the monochloride salt of the cationic coordination complex [CoCl2(en)2]+. One chloride ion in this salt readily undergoes ion exchange but the two other chlorides are less reactive, being bound to the metal center. The more stable cis-dichlorobis(ethylenediamine)cobalt(III) chloride is also known.

Cobalt(III) chloride or cobaltic chloride is an unstable and elusive compound of cobalt and chlorine with formula CoCl
3
. In this compound, the cobalt atoms have a formal charge of +3.

Transition metal amino acid complexes are a large family of coordination complexes containing the conjugate bases of the amino acids, the 2-aminocarboxylates. Amino acids are prevalent in nature, and all of them function as ligands toward the transition metals. Not included in this article are complexes of the amides and ester derivatives of amino acids. Also excluded are the polyamino acids including the chelating agents EDTA and NTA.

<span class="mw-page-title-main">Carbonatobis(ethylenediamine)cobalt(III) chloride</span> Chemical compound

Carbonatobis(ethylenediamine)cobalt(III) chloride is a salt with the formula [CoCO3(en)2]Cl (en = ethylenediamine). It is a red diamagnetic solid that is soluble in water. It is the monochloride salt of a cationic carbonate complex [CoCO3(en)2]+. The chloride ion in this salt readily undergoes ion exchange. The compound is synthesized by the oxidation of a mixture of cobalt(II) chloride, lithium hydroxide, and ethylenediamine in the presence of carbon dioxide:

Cobalt compounds are chemical compounds formed by cobalt with other elements.

<span class="mw-page-title-main">Sodium tris(carbonato)cobalt(III)</span> Chemical compound

Sodium tris(carbonato)cobalt(III) is the inorganic compound with the formula Na3Co(CO3)3•3H2O. The salt contains an olive-green metastable cobalt(III) coordination complex. The salt, a homoleptic metal carbonato complex, is sometimes referred to as the “Field-Durrant precursor” and is prepared by the “Field-Durrant synthesis”. It is used in the synthesis of other cobalt(III) complexes. Otherwise cobalt(III) complexes are generated from cobalt(II) precursors, a process that requires an oxidant.

References

  1. A. Werner (1912). "Zur Kenntnis des asymmetrischen Kobaltatoms. V". Chemische Berichte . 45 (1): 121–130. doi:10.1002/cber.19120450116.
  2. Jack M. Harrowfield; Mark I. Ogden; Brian W. Skelton; Allan H. White (2005). "Alfred Werner Revisited: Some Subtleties of Complex Ion Synthesis and Isomerism". Comptes Rendus Chimie. 8 (2): 121–128. doi:10.1016/j.crci.2004.10.013. hdl: 20.500.11937/8231 .
  3. 1 2 D. Witiak, J. C. Clardy, and D. S. Martin, Jnr. (1972). "The Crystal Structure of (+)-D-Tris(ethylenediamine)cobalt(III) Nitrate". Acta Crystallographica . B28 (9): 2694–2699. Bibcode:1972AcCrB..28.2694W. doi:10.1107/S056774087200679X.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  4. J. A. Broomhead; F. P. Dwyer; J. W. Hogarth (1960). "Resolution of the Tris(Ethylenediamine)Cobalt(III) Ion". Inorganic Syntheses. Vol. VI. pp. 183–186. doi:10.1002/9780470132371.ch58. ISBN   978-0-470-13237-1.
  5. Girolami, G. S.; Rauchfuss, T. B. and Angelici, R. J., Synthesis and Technique in Inorganic Chemistry, University Science Books: Mill Valley, CA, 1999 ISBN   0-935702-48-2
  6. von Zelewsky, A. "Stereochemistry of Coordination Compounds" John Wiley: Chichester, 1995 ISBN   047195599X.