Coordination Compounds 1.

Coordination Compounds Complex compounds in which transition metal atoms are bound to a number of anions or neutral molecules 2. Coordination Entity :Constitutes a central metal atom or ion bonded to a fixed number of ions or molecules Example: [CoCl3(NH3)3] is a coordination entity 3. Central Atom or Ion: The atom or ion to which a fixed number of ions/groups are bound in a definite geometrical arrangement around it in a coordination entity Example: Ni2+ in [NiCl2(H2O)4] and Fe3+ in [Fe(CN)6]3 4. Ligands : Ions or molecules bound to the central metal atom or ion in a coordination entity Types of ligands a) Unidentate. When a ligand is bound to a metal ion through a single donor atom, as with Cl, H2O or NH3, the ligand is said to be unidentate. b) Didentate When a ligand can bind through two donor atoms as in H2NCH2CH2NH2 (ethane-1,2-diamine) or C2O42 (oxalate), the ligand is said to be didentate c) Polydentate. when several donor atoms are present in a single ligand, the ligand is said to be polydentate.

Ethylenediaminetetraacetate ion (EDTA4) is an important hexadentate ligand. It can bind through two nitrogen and four oxygen atoms to a central metal ion. d) Ambidentate ligand Ligand which can ligate through two different atoms is called ambidentate ligand. Examples of such ligands are the NO2 and SCN ions. *NO2 ion can coordinate either through nitrogen or through oxygen to a central metal atom/ion.

*Similarly, SCN ion can coordinate through the sulphur or nitrogen atom.

5. Coordination Number : Number of ligand-donor atoms bonded directly to the metal. Example: The coordination number of Pt and Ni in *PtCl6+2 and *Ni(NH3)4+2+ are 6 and 4 respectively. 6. Coordination Sphere : The central atom or ion and the ligands attached to it are enclosed in square brackets, which are collectively known as the coordination sphere. 7. Example: In the complex K4*Fe(CN)6+, the coordination sphere is *Fe(CN)6+4. 8. Coordination Polyhedron : The spatial arrangement of the ligand atoms which are directly attached to the central atom or ion Example: Octahedral, square planar, tetrahedral 9. Oxidation Number of Central Atom: The charge it would carry if all the ligands are removed along with the electron pairs that are shared with the central atom 10. Example: Coordination number of copper in *Cu(CN)4+3 is 1. 11. Homoleptic and Heteroleptic Complexes a) Homoleptic Complexes in which the metal is bound to only one kind of donor group. Example: [Co(NH3)6]3+ b) Heteroleptic Complexes in which the metal is bound to more than one kind of donor groups. For example: [Co(NH3)4Cl2]+

Cl Br F I CN OH O N CH3COO NO3 NO2 ONO

-1 -1 -1 -1 -1 -1 -2 -3 -1 -1 -1 -1

Chloride Bromide Fluoride Iodide Cyanide Hydroxide Oxide Nitride Acetate Nitrate Nitrite Nitrite

Chlorido Bromido Fluorido Iodo Cyano Hydroxo Oxido Nitrido Acetato Nitrato Nitrito-N Nitrito-O

SCN NCS CO3 SO4 C2O4 ClO4 ClO3 NH3 H2O CO en CH3NH2 CH3CH2NH2 NO PPh3

-1 -1 -2 -2 -2 -1 -1 0 0 0 0 0 0 0 0

Thiocyanate Isothiocyanate Carbonate Sulphate oxalate perchlorate chlorate

Thiocyanato Isothiocyanato Carbonato Sulphato Oxalato Perchlorato chlorato Ammine Aqua Carbonyl Ethane-1,2-diamine Methyl amine Ethyl amine Nitrosyl Triphenyl phosphine

Naming of Mononuclear Coordination Compounds The following rules are followed while naming coordination compounds.

The cation is named first in both positively and negatively charged coordination entities. The ligands are named in alphabetical order before the name of the central atom/ion. Names of the anionic ligands end in o and those of neutral and cation ligands are the same. [Exceptions: aqua (H2O), ammine (NH3), carbonyl (CO), nitrosyl (NO)]

To indicate the number of the individual ligands, the prefixes mono, di, tri, etc., are used. If these prefixes are present in the names of ligands, then the terms bis, tris, tetrakis, etc., are used. For example, [NiCl2(PPh3)2] is named as dichlorobis(triphenylphosphine)nickel(II). Oxidation state of the metal is indicated by a Roman numeral in parentheses. If the complex ion is cation, then the metal is named as the element. For example, Fe in a complex cation is called iron and Pt is called platinum.

If the complex ion is anion, then the metal is named with ate ending. For example, Co in a complex anion, [Co(SCN)4]2 is called cobaltate. The neutral complex molecule is named as the complex cation.

IUPAC name of some coordination compounds are as follows:

[Ni(CO)4+ Tetracarbonlynickel(0) [Co(NH3)3(H2O)3]Cl3 Triamminetriaquachromium(III) chloride [Pt(NH3)2Cl(NO2)+ Diamminechloridonitrito-N-platinum(II) [CoCl2(en)2+Cl Dichloridobis(ethane-1,2-diammine)cobalt(III) chloride K2[Zn(OH)4+ Potassium tetrahydroxozincate(II)

Formulas of Mononuclear Coordination Compounds The following are the rules for writing the formulas.

The central atom is listed first. The ligands are then listed in the alphabetical order. Polydentate ligands are also listed in the alphabetical order. In the case of abbreviated ligands, the first letter of the abbreviation is used for determining the position of the ligands in the alphabetical order. The formula of the entire coordination entity is enclosed in square brackets. Ligand abbreviations and formulas for polyatomic ligands are enclosed in parentheses. There should be no space between the ligands and the metal within a coordination sphere. For the charged coordination entity, the charge is indicated outside the square brackets, as a right superscript, with the number before the sign. Example: [Fe(CN)6]3, [Cr(H2O)6]3+, etc. The charge of the cation(s) is balanced by the charge of the anion(s

Q) Write the formulas for the following coordination compounds: (i) Tetraamineaquachloridocobalt(III) chloride (ii) Potassium tetrahydroxozincate(II) Potassium trioxalatoaluminate(III)

(iv) Dichloridobis(ethane-1,2-diamine)cobalt(III) (v) Tetracarbonylnickel(0) A) (i) [Co(NH3)4(H2O)Cl]Cl2 (ii) K2[Zn(OH)4] (iii) K3[Al(C2O4)3] + (iv) [CoCl2(en)2] (v) [Ni(CO)4] Q) Write the IUPAC names of the following coordination compounds:

(i) [Pt(NH3)2Cl(NO2)] (ii) K3[Cr(C2O4)3] (iii) [CoCl2(en)2]Cl (iv) [Co(NH3)5(CO3)]Cl (v) Hg[Co(SCN)4] A) (i) Diamminechloridonitrito-N-platinum(II) (ii) Potassium trioxalatochromate(III) (iii) Dichloridobis(ethane-1,2-diamine)cobalt(III) chloride (iv) Pentaamminecarbonatocobalt(III) chloride (v) Mercury tetrathiocyanatocobaltate(III) Q)Write the formulas for the following coordination compounds: (i) Tetraamminediaquacobalt(III) chloride (ii) Potassium tetracyanonickelate(II) (iii) Tris(ethane1,2diamine) chromium(III) chloride (iv) Amminebromidochloridonitrito-N-platinate(II) (v) Dichloridobis(ethane1,2diamine)platinum(IV) nitrate (vi) Iron(III) hexacyanoferrate(II) Q) Write the IUPAC names of the following coordination compounds: (i) [Co(NH3)6]Cl3 (ii) [Co(NH3)5Cl]Cl2 (iii) K3[Fe(CN)6] (iv) K3[Fe(C2O4)3] (v) K2[PdCl4] (vi) [Pt(NH3)2Cl(NH2CH3)]Cl Q)Using IUPAC norms write the formulas for the following: (i) Tetrahydroxozincate(II) (vi) Hexaamminecobalt(III) sulphate (ii) Potassium tetrachloridopalladate(II) (vii) Potassium tri(oxalato)chromate(III) (iii) Diamminedichloridoplatinum(II) (viii) Hexaammineplatinum(IV) (iv) Potassium tetracyanonickelate(II) (ix) Tetrabromidocuprate(II) (v) Pentaamminenitrito-O-cobalt(III) (x) Pentaamminenitrito-N-cobalt(III) Q)Using IUPAC norms write the systematic names of the following: (i) [Co(NH3)6]Cl3 (iv) [Co(NH3)4Cl(NO2)]Cl (vii) [Ni(NH3)6]Cl2 2+ (ii) [Pt(NH3)2Cl(NH2CH3)]Cl (v) [Mn(H2O)6] (viii) [Co(en)3]3+ (iii) [Ti(H2O)6]3+ (vi) [NiCl4]2 (ix) [Ni(CO)4]

COORDINATION COMPOUNDS
Werners theory of coordination compounds
The main postulates of Werners theory (proposed by Werner in 1898), are as follows:

(i) In coordination compounds metals show two types of linkages (valancies), primary and secondary. (ii) The primary valancies are normally ionisable and are satisfied by negative ions. (iii) The secondary valancies are non-ionisable which are satisfied by negative ions or neutral molecules. The secondary valency is equal to the coordination number and is fixed for a metal. (iv) The ions/groups bound by the secondry linkages to the metal have characteristic spatial arrangements corresponding to different coordination numbers. Werner further postulated that the most common geometrical shapes of coordination compounds are octahedral, tetrahedral and square planar. What is the difference between a double salt and a complex? Although double salts as well as the complex compounds are formed by the combination of two or more stable compounds in stoichiometric ratio, the main difference between the two is that the double salt like Mohrs salt, potash alum, etc.

dissociate completely into simple ions when dissolved in water. On the other hand complex ions such , do not dissociate into ions.

COORDINATION COMPOUNDS
Nomenclature of coordination compounds
(i) Writing the formulas of coordination compound: According to International Union of Pure and Applied Chemistry (IUPAC), following rules are applied while writing the formulas of mononuclear (containing single central metal atom) coordination compounds:

(a) The central atom is listed first. (b) The ligands are then listed in alphabetical order without considering their charge. (c) Polydentate ligands are also written alphabetically. In case of abbreviated ligand, the first letter of abbreviation is used to determine the position of ligand in alphabetical order. (d) The formula of the entire coordination entity, whether charged or uncharged, is enclosed in square brackets. When ligands are polyatomic, their formulas are enclosed in parantheses. Ligand abbreviations are also enclosed in parantheses. For example,

(e) There should be no space between the ligands and the metal within a coordination sphere. (f) When the formula of a charged coordination entity is to be written without that of the counter ion, the charge is indicated outside the square brackets as a right superscript with the number before the sign. For example, etc. (g) The charge of cation(s) is balanced by the charge of anion(s). (ii) Writing the name of coordination compounds: As per IUPAC recommendations, following rules are adopted while naming the mononuclear coordination compounds: (a) The name of cation is written first in both positively and negatively charged coordination entities followed by the naming of anion. (b) The legands are named in an alphabetical order before the name of central atom/ion. (This procedure is opposite to that in writing formula). (c) Names of anionic legands and in O, those of cationic and neutral ligands are the same except aqua for , ammine for , carbonyl for CO and nitrosyl for NO. These are placed within closing marks [ ]. (d) Prefixes mono, di, tri, etc., are used to indicate the number of the individual ligands in the coordination entity. When the names of the ligands include a numerical prefix, then the terms, bis, tris, tetrakis are used, the ligand to which they refer being placed in parenthesis. For example, is named as dichlorobis(triphenylphosphine) nickel (II). (e) Oxidation state of the metal in cation, anion or neutral coordination entity is indicated by roman numerical in parenthesis. (f) If the complex ion is a cation, the metal is named same as the element. For example, Co in a complex cation is called cobalt and Pt is called platinum. If the complex ion is an anion, the name of the metal ends with the suffix- ate. For example, Co in a complex anion, is called cobaltate. For some metals, the latin names are used in the complex anions, e.g., ferrate for Fe.

(g) The neutral complex molecule is named similar to that of the complex cation. Note: IUPAC recommendations (2004) Within the complex ion, the formulas of all the ligands will be listed alphabetically according to their names irrespective of the charge on them. Anionic legands will end with-ido so that fluoro, chloro, bromo, iodo would become fluorido, chlorido, bromido, iodido respectively. Let us take some examples for better understanding the naming of coordination compounds. Example 1. Name the following compounds: (i) (ii) (iii) (iv) Solution (i) Name: Tris(ethane-1, 2-diammine)cobalt (III) sulphate Reason: In this molecule, the counter anion is the sulphate and three sulphates are bonded with two complex cations. So, the charge on each complex cation must be +3. Further, ethane-1, 2-diammine is a neutral molecule, hence the oxidation number of cobalt in the complex ion is +3. (ii) Name: Pentaamminechloroplatinum (IV) bromide Reason: This complex ion is a cation with counter anions, the bromides. The charge on the complex ion must be +3 because it bonds with three bromides. The is a neutral molecule and the chloride carries 1 charge. Hence the oxidation number of platinum is +4. (iii) Name: Potassium hexacyanoferrate (II) Reason: Since there are binding with a complex ion, the charge on the complex ion must be 4. Since each ligand (CN) carries-1 charge, the oxidation number of Fe must be +2. The common name of this compound is potassium ferrocyanide. (iv) Name: triamminetriaquachromium (III) chloride Reason: Here the complex ion inside the square bracket is a cation because the counter ion, (i.e. chloride ion) is anion. Since the compound is electrically neutral and the charge on three chloride ions is 3, the charge on complex ion must be +3. All the ligands are neutral molecules hence the oxidation number on chromium must be equal to the charge on complex ion, +3. The amine ligands are named before the aqua ligands according to alphabetical order. Example 2. Write the molecular formulas of the following coordination compounds: (i) Potassium tetrahydroxozincate(II) (ii) Diamminechloridonitrito-N-platinum(II) (iii) Tetraammineaquachloridocobalt(III) chloride (iv) Potassium trioxalatoaluminate(III) Solution (i) (ii) (iii) (iv)

Coordination Compounds

Isomerism in coordination compounds Isomers are those compounds which have the same chemical formula but different structural arrangements of their atoms. Different arrangement of atoms due to their different structures are responsible for their different physical or chemical properties. Broadly two types of isomerisms are shown by coordination compounds which can be further classified as follows:

1. Stereoisomerism: Stereoisomers have the same chemical formula and chemical bonds but they have different special arrangements. In coordination compounds, these isomers arise due to stereochemical deposition of their ligands. They are further classified as follows: (i) Geometrical isomerism: This type of isomerism arises in heteroleptic coordination complexes due to different possible geometric arrangements of the ligands. When similar ligands are adjacent to each other, they form cis isomer and when they are opposite to each other a trans isomer is formed. For example, platinum ammine complexes are geometrical isomers, as described below:

Geometrical isomerism is very common in complexes with coordination number 4 and 6. The best example of geometrical isomerism in octahedral complexes is provided by the violet and green form of ion.

Another type of geometrical isomerism occurs in octahedral coordination compounds are, the facial (fac) o and meridional (mer) isomer (see following figure)

(ii) Optical isomerism: Optical isomerism arises due to absence of elements of symmetry (plane of symmetry or axis of symmetry) in the complex. Optical isomers or enantiomers are the mirror images that cannot be superimposed on one another. The molecules or ions that cannot be superimposed are called chiral. A chiral molecule is an optically active and has the property of rotating the plane of polarized light either to its left (called laevo) or to its right (called dextro). If polarized light remains undeflected, the compound is inactive or racemic (i.e., mixture of 50% laevo and 50% dextro). Optical isomerism is common in octahedral complexes involving didentate ligands.

In a coordination compound of the type (see the figure below).

only the cis-isomer shows optical activity

2. Structural isomerism: Structural isomers have same chemical formula but they possess different types of bonds. These types of isomers also differ in the extent of ionization, position of ligands, etc. These are further classified as follows: (i) Linkage isomerism: This type of isomerism arises in the coordination compounds containing ambidentate ligands. An ambidentate ligand can link with the metal atom/ion in two different ways. So two types of structures are formed, called linkage isomers. For example, in the complex , nitrite ligand is bound to the metal in two different ways as follows:

(ii) Ionisation isomerism: When the counter ion in a complex salt acts as a ligand and the ligand of the complex becomes counter ion (i.e., a mutual exchange between counter ion and ligand), the two forms of the complex are called ionisation isomers and the process is called ionisation isomerism. For example,

(iii) Coordination isomerism: When there is an interchange between cationic and anionic species of different metal ions and the ligands present in a complex, this type of isomerism arises. For example,

Here, the ligand

is bound to

metal cation in one complex while it is bound to is bound to

in

its coordination isomer. Similarly, the ligand coordination isomer it is bound to ion.

ion in one complex and in its

(iv) Solvate isomerism: It is known as hydrate isomerism when water is the solvent. In solvate isomers solvent molecules are either directly bound to the metal ion or may be present as free solvent molecules in the crystal lattice. For example,

Example 3. Indicate the types of isomerism exhibited by the following complexes and draw the structures for these isomers : (i) (ii) (iii) (iv) Sol. (i) (a) Both geometrical (cis-trans) and optical isomers for cis can exist.

(b) Optical isomers (d- and l-) of cis

(ii) Two optical isomers can exist. (iii) Ionisation isomers :

Linkage isomers :

There are 10 possible isomers (geometrical, ionisation and linkage isomers are possible). (iv) Geometrical (cis-, trans-) isomers can exist.

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