coordination compounds complex ions. coordination compounds cocl 3 6nh 3 [co(nh 3 ) 6 ]cl 3 alfred...
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COORDINATION COMPOUNDS
COMPLEX IONS
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COORDINATION COMPOUNDS
CoCl3 6NH3
[Co(NH3)6]Cl3
Alfred Werner introduced the 2 types of valences:
1) Primary valence – oxidation number/charge2) Secondary valence – coordination number
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COMPLEXES
• Metal – usually transition metal either NEUTRAL or POSITIVELY CHARGED acting as LEWIS ACID
• Ligand – usually has at least one pair of unshared valence electrons and acts as LEWIS BASE
Metal-Ligand interaction forms a COORDINATE COVALENT BOND
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LIGANDS
• DENTICITY (monodentate, bidentate, polydentate)
• CHELATING AGENTS (for bi/polydentate ligands)
• FIRST COORDINATION SPHERE as signified by []
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EXAMPLES
1) [Cu(NH3)2(H2O)Cl]+
2) [Fe(H2O)2(CN)4]-
3) [Ni(H2NCH2CH2NH2)2]2+
Identify Primary Valence and Secondary Valence
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NOMENCLATURE
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RULES
• Cation Before Anion• Ligand before Central
Metal, reverse for formula
• Ligand Anions end in –o/-ido
• Neutral ligands retain their names
• Special Ligand Names
• [Co(en)3]Cl3, K2[CoCl4]
• Cl- • ethylenediamine• H2O, NH3, CO, NO
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RULES
• Greek prefixes (di/bis)• Oxidation number in
Roman numeral after the Metal Name
• If complex is anion, end in –ate added to Latin name
• For multiple ligands, use alphabetical order regardless of prefix
• [CoCl4]2-, [Ni(en)2]2+
• [Co(NH3)3(NO2)3]
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EXAMPLE
• [Ni(CO)4]
• [Co(H2O)4Cl2]Cl
• Na3[Ag(S2O3)2]
• [Fe(en)3](NO3)3
• [Cr(NH3)4[FeF6]2
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SEATWORK
• [Ag(NH3)2]Cl
• [Co(NH3)3Cl3]
• K4[Fe(CN)6]
• [Ni(CO)4]
• [Cu(en)2]SO4
• [Pt(NH3)][PtCl6]
• [CoCl(NH3)4(H2O)]Cl2
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STRUCTURAL ISOMERS
-compounds of same empirical formula but with different arrangement
4 TYPES- Ionization {[Co(NH3)5(SO4)]Br, [Co(NH3)5Br]SO4}
- Hydrate {[Cr(H2O)6]Cl3, [Cr(H2O)5Cl]Cl2H2O}
- Linkage {-NO2, -ONO}
- Coordination {[Cu(NH3)4][PtCl4], [Pt(NH3)4][CuCl4]}
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STEREOISOMER
-with different spatial arrangement• GEOMETRIC – cis and trans {Co(NH3)4Cl}• OPTICAL – nonsuperimposable mirrors of each
other
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VALENCE BOND THEORY
• Bond is formed with overlap of two orbitals• For complexes: overlap of ligand orbital
(containing an electron pair) and a metal orbital (empty)
• Number of Ligands GEOMETRY • Linear (2), Square Planar (4), Tetrahedral (4),
Octahedral (6)
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EXAMPLES
OCTAHEDRAL COMPLEXES• [Cr(H2O)6]3+ (outer orbital complex)
• [FeF6]3- (inner orbital complex)
SQUARE PLANAR• [Ni(CN)4]2-
TETRAHEDRAL• [CoCl4]2-
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CRYSTAL FIELD THEORY
• Electrostatic attraction (between metal and ligand)• Electrostatic repulsion (between electrons sharing
an orbital)• Electrical repulsion is dependent on orientation of d
orbitals and the incoming ligands causing splits in energy
• crystal field splitting (Δ) – dependent on metal and nature of ligand, affects color and magnetic properties
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GEOMETRY
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OCTAHEDRAL COMPLEX
___ ___
___ ___ ___
___ ______ ___ ___
Δ(high)
eg
t2g
Δ(low)eg
t2g
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TETRAHEDRAL COMPLEX
___ ___ ___
___ ___Δ(high)
t2g
eg
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SQUARE PLANAR COMPLEX
___
___
___
___ ___
d x2-y
2
d xy
d z2
d xz d yz
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SPECTROCHEMICAL SERIES
Order of ligands based on ability to produce large Δ (strong field vs weak field)
I-<Br-<Cl-<F-<OH-<H2O<NH3<en<NO2-<CN-
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PARAMAGNETISM and COLOR
• Presence of unpaired electrons of the metal• May usually lead to colored complexes
E = hc/λ• Fe3+ in [Fe(H2O)6]3+ vs Ca2+ or Cd2+
• [Fe(CN)6]3- vs [FeF6]3-
• [CoCl6]3- vs [Co(NH3)6]3+
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SAMPLE PROBLEM
A compound contains 21.35% Cr, 28.70% N, 6.209% H and 43.68%Cl by mass.
(a) It does not react with HCl.(b) On reaction with AgNO3, it gives 2 moles of AgCl per
mole of compound.(c) It has an electrical conductivity corresponding to
3mols of ions per mole of compound.1. Give the inferences of a, b and c.2. Write the formula and give the name of the
compound.