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Chemistry of Coordination Compounds
Chemistry of Coordination Compounds
Chapter 24
Chemistry of Coordination Compounds
Coordination Compounds
Complex ion: [Cu(NH3)4]2+
Coordination compound: K2CuCl4
Complex ion: [CuCl4]2
Examples in nature:
heme
chlorophyll
enzymes
Industrial catalysts; agents in electroplating baths; extraction of metals from ores
CoCl3.nNH3
Consider
with n = 4, 5, 6
How can we have compounds with these various compositions?
Dissolve in water and add AgNO3. Some Cl precipitates as AgCl immediately, some
much more slowly. This indicates the relative number of Cl that are ionic or covalent.
Composition
Color
No. Cl pptd Formula
.
CoCl3 6NH3
yellow
3
[Co(NH3)6]Cl3
CoCl3.5NH3
purple
2
[Co(NH3)5Cl]Cl2
CoCl3.4NH3
green
1
[Co(NH3)4Cl2]Cl
CoCl3.4NH3
violet
1
[Co(NH3)4Cl2]Cl
The green and violet compounds must have some further difference.
CoCl3.nNH3,
24-1
Chapter 24
2
OH
hydroxo
O
oxo
F
fluoro
Cl
chloro
Br
bromo
I
iodo
CN
cyano
NC
isocyano
NCS
isothiocyanato
SCN
thiocyanato
SO42
sulfato
NO3
nitrato
NO2
nitro
ONO
nitrito
CO32
carbonato
H2NCH2CH2NH2
ethylenediamine
24-2
Chapter 24
Redox Reactions
Inner Sphere
[Co(NH3)5Cl]2+ + [Cr(H2O)6]2+ + 5H2O [Cr(H2O)5Cl]2+ + [Co(H2O)6]2+ + 5NH3
Cl is transferred from Co to Cr
[Cr(H2O)5NC]2+ was prepared this way:
[Co(NH3)5CN]2+ + [Cr(H2O)6]2++ 5H2O fast> [Cr(H2O)5NC]2+ + [Co(H2O)6]2+ + 5NH3
[Cr(H2O)5NC]2+ 30 sec> [Cr(H2O)5CN]2+
Substitution Reactions
Replace one ligand with another
Solid state reactions can be accomplished by heating
[Co(NH3)5(H2O)]Cl3 [Co(NH3)5Cl]Cl2 + H2O
In solution, we can replace one ligand by another (aquation or anation or direct
substitution)
[Co(NH3)5Cl]2+ + H2O [Co(NH3)5(H2O)]3+ + Cl
aquation
[Co(NH3)5(H2O)]3+ + NCS [Co(NH3)5NCS]2+ + H2O anation
direct substitution
[PtCl4]2 + NH3 [PtCl3NH3] + Cl
24.2 Chelates
Monodentate: attached at only one atom
Polydentate: attached at two or more separated atoms
ethylenediamine (en): NH2CH2CH2NH2 attaches at the two nitrogen atoms
ethylenediaminetetraacetic acid (EDTA): (HOOCCH2)2NCH2CH2N(CH2COOH)2
attaches at up to six positions
called a chelate
Chelating Ligands
24-3
Chapter 24
Chelate Effect
Chelating ligands give much larger values of formation constants
[Ni(H2O)6]2+ + 6NH3 ! [Ni(NH3)6]2+ + 6H2O
Kf = 4 108
[Ni(H2O)6]2+ + 3en ! [Ni(en)3]2+ + 6H2O
Kf = 2 1018
Sequestering agents are chelating agents that are used to remove unwanted metal ions.
In medicine sequestering agents are used to selectively remove toxic metal ions (e.g.
Hg2+ and Pb2+) while leaving biologically important metals.
(EDTA4).
Chelating Ligands
One very important chelating agent is ethylenediaminetetraacetate EDTA is used
to tie up Ca2+ in bathroom cleaners, shower sprays
to prevent blood clots
to remove heavy metals from the body when poisoned
to solubilize iron in plant fertilizer
to remove the iron taste from mayonnaise (arising from its preparation in iron vats)
24-4
Chapter 24
Nomenclature
Apply the rules to the following compounds.
[Cr(H2O)5Cl]SO4
pentaaaquachlorochromium(III) sulfate
2+
[Cr(H2O)5Cl]
pentaaquachlorochromium(III) ion
[Cr(H2O)4Cl2]Cl
tetraaquadichlorochromium(III) chloride
[Cr(H2O)4Cl2]+
tetraaquadichlorochromium(III) ion
[Cr(NH3)3Cl3]
triamminetrichlorochromium(III)
K2[PtCl4]
potassium tetrachloroplatinate(II)
[PtCl4]2
tetrachloroplatinate(II) ion
dichlorobis(ethylenediamine)cobalt(III) chloride
[Co(en)2Cl2]Cl
tetraamminecopper(II) sulfate
[Cu(NH3)4]SO4
potassium hexacyanoferrate(II)
K4[Fe(CN)6]
hexaamminechromium(III) hexachloroiridate(III)
[Cr(NH3)6][IrCl6
diaquabromochlorofluoroiodochromate(III) ion
[Cr(H2O)2BrClFI]
Group Work: Name these compounds
[Co(NH3)4(H2O)F]2+
[Cu(en)2]2+
[Pt(NH3)Cl3]
[Cu(en)2][PtCl4]
24.3 Isomerism
Isomers two or more forms of a compound having the same composition
Isomers
Structural isomers (different bonding)
Coordination sphere
ionization isomer
isomers
hydration isomers
linkage isomers
Stereoisomers (identical bonding)
geometrical isomers
optical isomers
Structural Isomers
Different ligands or different attachment of ligands
Ionization Isomers exchange ion between ligand and anion
[Co(NH3)4ClBr]Cl and [Co(NH3)4Cl2]Br
[Pt(NH3)3Cl]NO2 and [Pt(NH3)3NO2]Cl
Group Work:
Write the formula of an ionization isomer of [Co(NH3)4(NO2)2]Br.
Hydration Isomers exchange water as ligand and hydrate
[Cr(H2O)6]Cl3, [Cr(H2O)5Cl]Cl2.H2O, and [Cr(H2O)4Cl2]Cl.2H2O
[Co(NH3)5(H2O)]Cl3 and [Co(NH3)5Cl]Cl2.H2O
24-5
Chapter 24
Group Work:
Write the formula of a hydration isomer of [Pt(NH3)4Cl2]Cl.H2O
Linkage Isomers ligands that can bond at more than one atomic site (ambidentate)
:CN and :NC
[Cr(H2O)5CN]2+ and [Cr(H2O)5NC]2+
:NCS and :SCN
[Co(NH3)5NCS]2+ and [Co(NH3)5SCN]2+
:NO2 and :ONO
[Pt(NH3)3NO2]+ and [Pt(NH3)3ONO]+
Group Work:
Write the formula of a linkage isomer of [Co(NH3)5NCO]2+
Geometrical Isomers
Different orientations of ligands within a given geometry
Square planar and octahedral structures with two different ligands can have like ligands
adjacent (cis) or opposite (trans) one another
[Co(NH3)4Cl2]+
[Co(en)2Cl2]+
trans-[Co(NH3)4Cl2]+
cis-[Co(NH3)4Cl2]+
Octahedral Complexes
Chapter 24
Optical isomers are mirror images of one another that cannot be superimposed.
Check for optical isomers by checking superpositions of mirror images (rotate to
superimpose)
Group Work
Which of these have optical isomers?
cis [Co(NH3)4Cl2]+
trans[Co(NH3)4Cl2]+
cis[Co(en)2Cl2]+
trans[Co(en)2Cl2]+
[Co(en)Cl4]
[Co(en)3]2+
[Cu(en)Cl2]
Tetrahedral can have optical isomers if all four ligands are different.
Does tetrahedral MA2B2 have optical isomers?
24-7
Chapter 24
Hybrid Orbitals
Octahedral hybridization uses s, px, py, pz, dx2y2, dz2 atomic orbitals to form six d2sp3
hybrid orbitals
Consider the electron configurations.
Fe [Ar]3d64s2
Fe3+ [Ar]3d53s0
24-8
Chapter 24
To form [Fe(CN)6]3, need 6 empty orbitals to hold the electron pairs donated by the C
atoms, so must pair up 2 electrons:
Now we can form bonds with two d orbitals, one s orbital, and three p orbitals, giving
d2sp3 hybridization.
CN-
CN-
F- F-
F- F-
F- F-
Group Work
Write box diagrams for the electron configuration of Cr(III), using high spin and low
spin arrangements of 6 ligands.
Would there be two arrangements for Cr(III)?
Group Work
Consider the electron configurations for Co
Co [Ar]3d74s2
24-9
Chapter 24
Toward Ligands
dz2
dx2y2
The splitting of the energy levels is called , the crystal field splitting energy.
Not all d electrons have the same energy.
It is possible to promote an electron from a lower energy orbital to a higher energy
orbital, with absorption of light of a wavelength corresponding to an energy of .
24-10
Chapter 24
Electron occupancy varies with the ligand only for the following electron
configurations: d4, d5, d6, d7
Other configurations give identical results for strong or weak field ligands.
Tetrahedral are smaller than octahedral; as a result, there are no ligands that are known
24-11
Chapter 24
24-12