Chapter 1: Matter and Measurement - chemistryworkshopjr

Chapter 1: Matter and Measurement - chemistryworkshopjr

Coordination Chemistry NARESH PARSAD PGT-CHEMISTRY KV NHPC DHARCHULA Werner/Jorgensen Controversy Sophus Jorgensen Alfred Werner

Probably the greatest conceptual contribution to inorganic chemistrycomparable in both direct and indirect impact to the concept of the tetrahedral carbon atom in organic chemistryis Alfred Werners concept of coordination compounds and his general theory of how they behave. Albert Cotton Werners Theory of Coordination Compounds

CoCl3 and NH3. [Co(NH3)6]Cl3 and [CoCl (NH3)5]Cl2 Alfred Werner 1866-1919 Werners theory of Coordination Compounds Werner in 1898, propounded his theory of coordination compounds. The main postulates are: 1. In coordination compounds metals show two types of linkages

(valences)-primary and secondary. 2. The primary valences are normally ionisable and are satisfied by negative ions. 3. The secondary valences are non ionisable. These are satisfied by neutral molecules or negative ions. The secondary valence is equal to the coordination number and is fixed for a metal. 4. The ions/groups bound by the secondary linkages to the metal have characteristic spatial arrangements corresponding to different coordination numbers.

Werners Experiment As a 26 year old lecturer Werner did the following experiment Empirical formula Co(Cl)3(NH3)6 # Cl- ions Complex ions Ag+ ppt 4

3 Orange/yellow Co(Cl)3(NH3)5 + 3 Cl3 2 purple

Co(Cl)3(NH3)4 Green/violet [Co(NH3)6]3+ [Co(NH3)5Cl]2+ + 2 Cl- 2 1

[Co(NH3)4Cl2]1+ + 1 Cl- Wener proposed that metals exhibit both primary and secondary valences It was found that some of the chloride ions could be precipitated as AgCl on adding excess silver nitrate solution in cold but some remained in solution.

1 mol 1 mol 1 mol 1 mol CoCl3.6NH3 (Yellow) CoCl3.5NH3 (Purple) CoCl3.4NH3 (Green) CoCl3.4NH3 (Violet)

gave 3 mol AgCl gave 2 mol AgCl gave 1 mol AgCl gave 1 mol AgCl Werners Theory Two types of valence or bonding capacity. Primary valence (oxidation number). Based on the number of e- an atom loses in forming the ion.

Secondary valence (coordination number). Responsible for the bonding of other groups, called ligands, to the central metal atom. [Co(NH3)6]Cl3 [Co(NH3)6]3+ + 3 Cl[CoCl(NH3)5]Cl2 [CoCl(NH3)5]2+ + 2 Cl- Q . A complex is prepared by mixing COCl3 and NH3 in the molar ratio of 1 : 4, 0.1 M solution of this complex was found to freeze at 0.372 C. What is the formula of the complex ? Given that molal

depression constant of water Kf = 1.86 C/m. Ans. Theoretical Tf = Kf . mTf = Kf . m = 1.86 0.1 = 0.186 observed Tf = Kf . mTf = 0.372 i= 0.372/0.186 = 2 As observed Tf = Kf . mT is double of the theoretical value this shows that

each molecule of the complex dissociates to form two ions. formula is : [CO (NH3)4 Cl2]Cl Difference between a double salt and a complex Both double salts as well as complexes are formed by the combination of two or more stable compounds in stoichiometric ratio. However, they differ in the fact that double salts such as carnallite, KCl.MgCl2.6H2O, Mohrs salt, FeSO4.(NH4)2SO4.6H2O, potash alum, KAl(SO4)2.12H2O, etc. dissociate into simple ions completely when dissolved in water. However, complex ions such as [Fe(CN)6]4 of

K4Fe(CN)6, do not dissociate into Fe2+ and CN ions. Double Salts Complexes They do not dissociate

in to simple Ions when dissolved in water Example: K4[Fe(CN)6] contains a central metal atom or ion surrounded by number of oppositely charged ions or neutral molecules-(Ligands).

They dissociate into simple ions when dissolved in water. Ex:FeSO4.(NH4)2SO4.6H2O (Mohrs salt) two salts are crystallised together in stoichiometric ratio from their saturated solution they are called double salts

Definitions of Some Important Terms Pertaining to Coordination Compounds (a) Coordination entity A coordination entity constitutes a central metal atom or ion bonded to a fixed number of ions or molecules. For example, [CoCl3(NH3)3] is a coordination entity in which the cobalt ion is surrounded by three ammonia molecules and three chloride ions. Other examples

are [Ni(CO)4], [PtCl2(NH3)2], [Fe(CN)6]4, [Co(NH3)6]3+. (b) Central atom/ion In a coordination entity, the atom/ion to which a fixed number of ions/groups are bound in a definite geometrical arrangement around it, is called the central atom or ion. For example, the central atom/ion in the coordination entities: [NiCl2(H2O)4], [CoCl(NH3)5]2+ and [Fe(CN)6]3 are Ni2+, Co3+ and Fe3+, respectively. These central atoms/ions are also referred to as Lewis acids.

(c) Ligands The ions or molecules bound to the central atom/ion in the coordination entity are called ligands. These may be simple ions such as Cl, small molecules such as H2O or NH3, larger molecules such as H2NCH2CH2NH2 or N(CH2CH2NH2)3 or even macromolecules, such as proteins. 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.

When a ligand can bind through two donor atoms as in H2NCH2CH2NH2 (ethane-1,2-diamine) or C2O4 2 (oxalate), the ligand is said to be didentate and when several donor atoms are present in a single ligand as in N(CH2CH2NH2)3, 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. When a di- or polydentate ligand uses its two or more donor atoms to bind a single metal ion, it is said to be a chelate ligand. The number of

such ligating groups is called the denticity of the ligand. Such complexes, called chelate complexes tend to be more stable than similar complexes containing unidentate ligands. Chelation Metals are able to bind or chelate (greek to claw) to other molecules or ions in solution called ligands Common Ligands are Lewis bases (electron pair donors) Monodentate

H N H H Bidentate H

N CH2CH2 N H H H Common Metal ions are Lewis acids (electron pair acceptors)

Coordinate Covalent bonds are formed L M Complexes using polydentate ligands are called chelates Table 24.3 Some Common Polydentate Ligands (Chelating Agents) 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. (d) Coordination number The coordination number (CN) of a metal ion in a complex can be defined as the number of ligand donor atoms to which the metal is directly bonded. For example, in the complex ions, [PtCl6]2 and [Ni(NH3)4]2+, the coordination number of Pt and Ni are 6 and 4 respectively. Similarly, in the complex ions, [Fe(C2O4)3]3 and [Co(en)3]3+, the coordination number of both, Fe and Co, is 6 because

C2O4 2 and en (ethane-1,2-diamine) are didentate ligands. It is important to note here that coordination number of the central atom/ion is determined only by the number of sigma bonds formed by the ligand with the central atom/ion. Pi bonds, if formed between the ligand and the central atom/ion, are not counted for this purpose. (e) Coordination sphere The central atom/ion and the ligands attached to it are enclosed in square bracket and is collectively termed as the

coordination sphere. The ionisable groups are written outside the bracket and are called counter ions. For example, in the complex K4[Fe(CN)6], the coordination sphere is [Fe(CN)6]4 and the counter ion is K+. (f) Coordination polyhedron The spatial arrangement of the ligand atoms which are directly attached to the central atom/ion defines a coordination polyhedron about the central atom. The most common coordination polyhedra are octahedral, square planar and tetrahedral. For example, [Co(NH3)6]3+

is octahedral, [Ni(CO)4] is tetrahedral and [PtCl4]2 is square planar. Fig. 9.1 shows the shapes of different coordination polyhedra. (g) Oxidation number of central atom The oxidation number of the central atom in a complex is defined as the charge it would carry if all the ligands are removed along with the electron pairs that are shared with the central atom. The oxidation number is represented by a Roman numeral in parenthesis following the name of the coordination entity. For example, oxidation number of copper in [Cu(CN)4]3 is +1 and it is written as Cu(I).

(h) Homoleptic and heteroleptic complexes Complexes in which a metal is bound to only one kind of donor groups, e.g., [Co(NH3)6]3+, are known as homoleptic. Complexes in which a metal is bound to more than one kind of donor groups, e.g., [Co(NH3)4Cl2]+, are known as heteroleptic. Formulas of Mononuclear Coordination Entities (i) The central atom is listed first. (ii) The ligands are then listed in alphabetical order. The placement of a ligand in the

list does not depend on its charge. (iii) Polydentate ligands are also listed alphabetically. In case of abbreviated ligand, the first letter of the abbreviation is used to determine the position of the ligand in the alphabetical order. (iv) The formula for the entire coordination entity, whether charged or not, is enclosed in square brackets. When ligands are polyatomic, their formulas are enclosed in parentheses. Ligand abbreviations are also enclosed in parentheses. (v) There should be no space between the ligands and the metal within a coordination sphere. (vi) 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, [Co(CN)6]3, [Cr(H2O)6]3+, etc. (vii) 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) (iii) Potassium trioxalatoaluminate(III)

(iv) Dichloridobis(ethane-1,2-diamine)cobalt(III) (v) Tetracarbonylnickel(0) Ans. (i) [Co(NH ) (H O)Cl]Cl (ii) K [Zn(OH) ] (iii) K [Al(C O ) ] 3 4 2

2 (iv) [CoCl (en) ] (v) [Ni(CO) ] 2 2 + 4

2 4 3 2 4

3 Naming of Mononuclear Coordination Compounds (i) The cation is named first in both positively and negatively charged coordination entities. (ii) The ligands are named in an alphabetical order before the name of the central atom/ion. (This procedure is reversed from writing formula). (iii) Names of the anionic ligands end in o, those of neutral and cationic ligands are the same except aqua for H2O, ammine for NH3, carbonyl for CO and nitrosyl for NO. These are placed within enclosing marks ( ).

(iv) 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 parentheses. For example, [NiCl2(PPh3)2] is named as dichlorobis(triphenylphosphine)nickel(II). (v) Oxidation state of the metal in cation, anion or neutral coordination entity is indicated by Roman numeral in parenthesis. (vi) 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.

Nomenclature In names and formulas of coordination compounds, cations come first, followed by anions. Anions as ligands are named by using the ending o. Normally: ide endings change to o. ite endings change to ito. ate endings change to ato.

Neutral molecules as ligands generally carried the unmodified name. If the complex is an anion the ending ate is attached to the name of the metal. Table 24.2 Some Common Monodentate Ligands. ide endings change to o

ate endings change to ato [Cr(NH3)3(H2O)3]Cl3 is named as: triamminetriaquachromium(III) chloride Explanation: The complex ion is inside the square bracket, which is a cation. The amine ligands are named before the aqua ligands according to alphabetical order. Since there are three chloride ions in the compound, the charge on the complex ion must be +3 (since the compound is electrically neutral). From the charge on the complex ion and the charge on the ligands, we can calculate the oxidation

number of the metal. In this example, all the ligands are neutral molecules. Therefore, the oxidation number of chromium must be the same as the charge of the complex ion, +3. [Co(H2NCH2CH2NH2)3]2(SO4)3 is named as: tris(ethane-1,2diammine)cobalt(III) sulphate Explanation: The sulphate is the counter anion in this molecule. Since it takes 3 sulphates to bond with two complex cations, the charge on each complex cation must be +3. Further, ethane-1,2 diamine is a neutral molecule, so the oxidation number of cobalt

in the complex ion must be +3. Remember that you never have to indicate the number of cations and anions in the name of an ionic compound. [Ag(NH ) ][Ag(CN) ] is named as: 3 2 2

diamminesilver(I) dicyanoargentate(I) Q. Write the IUPAC names of the following coordination compounds: (i) [Pt(NH ) Cl(NO )] (ii) K [Cr(C O ) ] (iii) [CoCl (en) ]Cl 3 2

2 3 2 4 3

2 2 (iv) [Co(NH ) (CO )]Cl (v) Hg[Co(SCN) ] 3 5 3

4 Ans. (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) Coordination Number

Ethylene Diamine EXAMPLE Relating the Formula of a Complex to the Coordination Number and Oxidation State of the Central Metal. What are the coordination number and oxidation state of Co in the complex ion [CoCl(NO2)(NH3)4]+? Solution: The complex has as ligands

1Cl, 1NO2, 4NH3 . The coordination number is 6. EXAMPLE Charge on the metal ion: Isomerism Werner predicted there would be only two isomers of [CoCl2(NH3)4]+ and mailed them to Jorgensen. He received the Nobel prize in 1913.

Isomerism The two or more compounds having same chemical formula but different structures are called isomers and the phenomenon is called isomerism Isomerism in Coordination Compounds (a) Stereoisomerism

(i) Geometrical isomerism (ii) Optical isomerism (b) Structural isomerism (i) Linkage isomerism (ii) Coordination isomerism (iii) Ionisation isomerism (iv) Solvate isomerism Stereoisomerism: Geometric Isomerism Geometric Isomerism

How many isomers would [CoCl3(NH3)3] have? Geometric Isomerism This type of isomerism arises in heteroleptic complexes due to different possible geometric arrangements of the ligands. Important examples of this behaviour are found with coordination numbers 4 and 6. In a square planar complex of formula

[MX2L2] (X and L are unidentate), the two ligands Xmay be arranged adjacent to each other in a cis isomer, or opposite to each other in a trans isomer Another type of geometrical isomerism occurs in octahedral coordination entities of the type [Ma3b3] like [Co(NH3)3(NO2)3]. If three donor atoms of the same ligands occupy adjacent positions at the corners of an octahedral face, we have the facial (fac) isomer. When the positions are around the meridian of the octahedron, we get the meridional (mer) isomer Geometric Isomerism

Optical Activity We are made up of chiral molecules l-amino acids, protein alpha helix, the DNA duplex, and sugars. dextrorotatory dlevorotatory l- Chirality or Handedness

Triethylenediamine cobalt(III) is a chiral molecule it differs only in how it interacts with another chiral object. You can not put a right handed glove on a left hand. Left and right circularly polarized light is an example of a chiral object. Optical Isomerism enantiomers

Optical Isomerism Optical isomers are mirror images that cannot be superimposed on one another. These are called as enantiomers. The molecules or ions that cannot be superimposed are called chiral. The two forms are called dextro (d) and laevo (l) depending upon the direction they rotate the plane of polarised light in a polarimeter (d rotates to the right, l to the left). Optical isomerism is common in octahedral complexes involving didentate ligands Optical Isomerism

Chiral shapes are not super imposable on their mirror image Examples of Structural Isomerism Ionization Isomerism [CrSO4(NH3)5]Cl pentaaminsulfatochromium(III) chloride [CrCl(NH3)5]SO4 pentaaminchlorochromium(III) sulfate

Coordination Isomerism [Co(NH3)6][CrCN6] hexaaminecobalt(III) hexacyanochromate(III) [Cr(NH3)6][CoCN6] hexaaminechromium(III) hexacyanocobaltate(III) Linkage Isomerism Linkage isomerism arises in a coordination compound containing

ambidentate ligand. A simple example is provided by complexes containing the thiocyanate ligand, NCS, which may bind through the nitrogen to give MNCS or through sulphur to give MSCN. Jrgensen discovered such behaviour in the complex [Co(NH3)5(NO2)]Cl2, which is obtained as the red form, in which the nitrite ligand is bound through oxygen (ONO), and as the yellow form, in which the nitrite ligand is bound through nitrogen (NO2). Linkage Isomerism

Coordination Isomerism This type of isomerism arises from the interchange of ligands between cationic and anionic entities of different metal ions present in a complex. An example is provided by [Co(NH3)6][Cr(CN)6], in which the NH3 ligands are bound to Co3+ and the CN ligands to Cr3+. In its coordination isomer [Cr(NH3)6][Co(CN)6], the NH3 ligands are bound to Cr3+ and the CN ligands to Co3+. Ionisation Isomerism

This form of isomerism arises when the counter ion in a complex salt is itself a potential ligand and can displace a ligand which can then become the counter ion. An example is provided by the ionisation isomers [Co(NH3)5SO4]Br and [Co(NH3)5Br]SO4. Solvate Isomerism This form of isomerism is known as hydrate isomerism in case where water is involved as a solvent. This is similar to ionisation isomerism. Solvate isomers differ by whether or not a solvent molecule is directly

bonded to the metal ion or merely present as free solvent molecules in the crystal lattice. An example is provided by the aqua complex [Cr(H2O)6]Cl3 (violet) and its solvate isomer [Cr(H2O)5Cl]Cl2.H2O (grey-green). Bonding in Complex Ions: Crystal Field Theory Consider bonding in a complex to be an electrostatic attraction between a positively charged nucleus and the electrons of the ligands.

Electrons on metal atom repel electrons on ligands. Focus particularly on the d-electrons on the metal ion. Octahedral Complex and d-Orbital Energies Electron Configuration in d-Orbitals P

Hunds Rule Pairing Energy Considerations Spectrochemical Series Large Strong field ligands CN- > NO2- > en > py NH3 > EDTA4- > SCN- > H2O > ONO- > ox2- > OH- > F- > SCN- > Cl- > Br- > ISmall

Weak field ligands Electron Configuration in d-Orbitals Effect of Ligands on the Colors of Coordination Compounds Absorption Spectrum max

Light Absorption and Transmission [Ni(H2O)6}2+ Transmitted Green Absorbed

(red) 700 nm o hc/small Ni(NH3)6]2+

[Ni(en)3]2+ Blue Purple (orange) 600 nm medium

(yellow) 570 nm large

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