Chapter 4

COORDINATION CHEMISTRY

Mar 15, 2017

https://www2.chemistry.msu.edu/courses/cem151/fall%202007/chap24lect_2007.ppt
RawatDAgreatt

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 Chapter 4 Reading
• Coordination chemistry
[2]: chapter 9-12
[1]: chapter 7, 21

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 Coordination chemistry
Contents and practice skills
• Structure • Have a basic understanding
• Naming about coordination
• Isomers chemistry

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 Coordination compounds
• Coordination compounds (complexes or complex ions)
– Metal atom/ion + ligand(s) (atoms, ions, or molecules)
– Ligands donate electrons to the metal  coordinate covalent bond
– Includes organometallic compounds (Metal –Carbon)

Ferrocene Fe(C5H5)2

cisplatin Heme B
chlorophyll a
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 A chemical mystery
Same metal, same ligands,
different colors, different number of ions when dissolved

1
2
3
4

3
1 2

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 Structure
Inner Coordination sphere: ligands covalently bound to the center metal
Outer sphere: free (labile); ionic binding

1
2
3
4

1
2

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 Structure
Inner Coordination sphere: ligands covalently bound to the center metal
Outer sphere: free (labile); ionic binding

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Oxidation state and coordination number
The most commonly encountered numbers are 4 and 6

1
2

The oxidation state of Co is (III) but the coordination number is 6

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 Geometries
• Coordination number of 4:
– Tetrahedral
– Square planar

Tetrahedral Square planar

• Coordination number of 6:
– Octahedral

Octahedral
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 Polydentate Ligands
Polydentate ligands or chelating agents: two or more donor atoms

• Ethylenediamine (en): NH2CH2CH2NH2,

bidentate (2 donor atoms)

• Ethylenediaminetetraacetate (EDTA),
has six donor atoms.

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 Polydentate Ligands

Chelating agents generally form more stable complexes than do monodentate ligands.
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 Chelating Agents

• Porphyrins are complexes

containing a form of the
porphine molecule
shown at right.

• Important biomolecules
like heme and chlorophyll
are porphyrins. chlorophyll a: tetradentate ligands

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Nomenclature of Coordination Compounds
• As always: cation name + anion name
• Inner sphere name:
Ligand name + metal + metal oxidation state (Roman numeral
in parentheses immediately after the name of the metal)
– Ligand names are alphabetically listed
– Prefixes denoting the number of a particular ligand are ignored when
alphabetizing.

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 Ligand name

• Anionic ligands end in “o”; neutral ligands: not changed

• If the complex is an anion, its ending is changed to -ate.

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 Naming Examples
• [Ag(NH3)2]Cl • K3[Fe(CN)6]
• diamminesilver(I) chloride • potassium hexacyanoferrate(III)
• [Pt(NH3)4]2+ • [Cu(NH3)4]SO4
• tetraammineplatinum(II) • tetraamminecopper(II) sulfate
• [PtCl4]2- • [Co(NH3)6]Cl3
• tetrachloroplatinate(II) • hexaamminecobalt(III) chloride
• [PtCl6]2- • [Co(NH3)4Cl2]+
• hexachloroplatinate(IV) • tetraamminedichlorocobalt(III)

• Pt(NH3)BrCl(CH3NH2)
• amminebromochloromethylamineplatinum(II)
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 Naming Examples
• [Ag(NH3)2]Cl • K3[Fe(CN)6]
• diamminesilver(I) chloride • potassium hexacyanoferrate(III)
• [Pt(NH3)4]2+ • [Cu(NH3)4]SO4
• tetraammineplatinum(II) • tetraamminecopper(II) sulfate
• [PtCl4]2- • [Co(NH3)6]Cl3
• tetrachloroplatinate(II) • hexaamminecobalt(III) chloride
• [PtCl6]2- • [Co(NH3)4Cl2]+
• hexachloroplatinate(IV) • tetraamminedichlorocobalt(III)

• Pt(NH3)BrCl(CH3NH2)
• amminebromochloromethylamineplatinum(II)
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Monodentate ligands

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Chelating amines

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Chelating ligands

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Chelating ligands

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 Ligand name
If the ligand itself is polydentate, (often) use bis-, tris-, etc., as prefix

tris(2,2-bipyridine)iron(II),
[Fe(C10H8N2)3]2+

dichlorobis(ethylenediamine)cobalt(III)
[Co(NH2CH2CH2NH2)2Cl2]+

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Practice

cis-diamminedichloroplatinum(II),

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Isomers

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Linkage isomers

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 Coordination-sphere isomers
• CrCl3(H2O)6
– [Cr(H2O)6]Cl3, The violet
– [Cr(H2O)5Cl]Cl2 ∙ H2O, The green
– [Cr(H2O)4Cl2]Cl ∙ 2 H2O, The (also) green

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 Stereoisomers
Geometric isomers

Just as a right hand will not fit into a left

glove, two enantiomers cannot be
superimposed on each other
Optical isomers or enantiomers

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 Enantiomers
• Most of the physical properties of chiral
molecules are the same, boiling point, freezing
point, density, etc.
• One exception is the interaction of a chiral
molecule with plane-polarized light.

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 Enantiomers
• If one enantiomer of a chiral compound is placed in a
polarimeter and polarized light is shone through it, the plane
of polarization of the light will rotate.
• If one enantiomer rotates the light 32° to the right, the other
will rotate it 32° to the left.

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Enantiomers

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DNA is needed for growth
and multiplication of cells.

Cisplatin damages the DNA

inside the cancer cells and
so prevents them from
multiplying.

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