Coordination Chemistry

1890’s: CoCl26H2O + NH3/NH4+

Reacted with Name (colour) Formula
H2O2 + act. Luteocobalt [Co(NH3)6]Cl3
charcoal chloride
H2O2 (only) Purpureocobalt [Co(NH3)5Cl]Cl2
chloride
Air, evapo- Praseocobalt trans-
S.M.Jørgensen rate with HCl chloride [Co(NH3)4Cl2]Cl
1837-1914 Heating the Violeocobalt cis-
green trans chloride [Co(NH3)4Cl2]Cl
15 February 2010 Coordination chemistry 1

Coordination number 6
Octahedral geometry

• Cobalt(III) ion in centre

• Donor atoms (N, Cl) in corners

Very common geometry in coordination

compounds
15 February 2010 Coordination chemistry 2

Coordination numbers
number geometry example

2 Linear Ag(NH3)2+

3 Trigonal planar Cu(CN)3-

4 Tetrahedral MCl4n-
Square planar PtCl42-
5 Trigonal bipyramide CuCl53-
Square pyramidal W(V)Cl4O-
15 February 2010 Coordination chemistry 3

1
 Coordination numbers
number geometry example

6 Octahedral Co(NH3)63+
Trigonal prismatic(rare) W(CH3)6
7 Capped or rare
Pentagonal bipyramide
8 Square antiprism Mo(CN)84-(aq)
dodecahedron Y(H2O)83+
9 Tricapped prismatic ReH9-
Pu(H2O)93+
15 February 2010 Coordination chemistry 4

Pu(H2O)93+

• (remember: aqua !)
15 February 2010 Coordination chemistry 5

Names and formula

• Cationic part first, anionic part next, water
of crystallisation etc. last

• From name to formula [ML1xL2yL3z…]]

Ligands alphabetic anionic, neutral, cationic

• From formula to name xL1yL2zL3…M

Ligands strictly alphabetic (x,y,z as prefixes)
M-ate if [----]n-

15 February 2010 Coordination chemistry 6

2
 Special ligand names
Name Formula Ligand name as ligand

water H2O aqua

ammonia NH3 ammine
( th l) i
(methyl)amine (CH3)NH2 ( th l) i
(methyl)amine
nitrogenmonoxide NO nytrosyl
carbonmonoxide CO carbonyl
dinitrogen N2 dinitrogen
dioxygen O2 dioxygen
15 February 2010 Coordination chemistry 7

Formula
• cis-Tetraaquadichlorochromium(III) chloride
• Potassium pentachloronitroosmate(IV)
• mer-trihydridotris(triphenylphosphin)ruthenium(III)
• Pentaamminechlorocobalt(III) nitrate
• Potassium trioxalatocobaltate(III)
• Bis(1,2-ethandiamine)diiodocobalt(III) perchlorate
• Dichlorobis(1,2-ethandiamine)cobalt(III) tetrafluoroborate
• Pentaamminedinitrogenruthenium(II) chloride
• Sodiumpentacyanonitrosylferrate(II) dihydrate
• Pentaamminecobalt(III)--cyanopentacyanocobaltate(III)

15 February 2010 Coordination chemistry 8

Names
• [PtCl2(NH3)2]
• [RhCl(NH3)5]Cl2
• [Co(NH3)6]SO4
• [Co(NH3)4(H2O)2](BF4)3
• Na3[Fe(CN)6] 2H2O,O
• [Ni(CO)4],
• [Co(CH3COO)BrCl(NH3)2],
• [Pt(py)4] [PtCl4],
• Na2[PdCl6],
• (NEt4)3[AlF6],
• [Pt(acac)2ClNH3]Cl
15 February 2010 Coordination chemistry 9

3
 Isomerism
Structural isomerism Stereoisomerism
(what is bound to what) (spatial arrangement)

Hydration Geometrical
Ionisation Optical
Linkage
Coordination
Polymerisation

15 February 2010 Coordination chemistry 10

Structural isomerism
Examples
• Ionisation Co(NH)5SO4Br
• Hydration Co(H2O)6Cl3
• Coordination CoCr(NH3)6(CN)6
• Linkage Co(NH3)5NO2Cl2
• Polymerisation PtCl2(NH3)2

15 February 2010 Coordination chemistry 11

Stereoisomerism
• Geometrical isomerism
– cis-trans
– fac-mer
– (tetrahedral-squareplanar)
(tetrahedral squareplanar)

• Optical isomerism
– enantiomers
– diastereomers

15 February 2010 Coordination chemistry 12

4
 Descriptors for chiral cases
• (+) - (-)
• d–l
• D-L
• R–S
• ∆-Λ
• δ–λ
Λ δ3

15 February 2010 Coordination chemistry 13

Coordination Chemistry
1890’s: CoCl26H2O + NH3/NH4+
Reacted with Name (colour) Formula
H2O2 + act. Luteocobalt [Co(NH3)6]Cl3
charcoal chloride
hl id
H2O2 (only) Purpureocobalt [Co(NH3)5Cl]Cl2
chloride
Air, evapo- Praseocobalt trans-
S.M.Jørgensen rate with HCl chloride [Co(NH3)4Cl2]Cl
1837-1914 Heating the Violeocobalt cis-
green trans chloride [Co(NH3)4Cl2]Cl
15 February 2010 Coordination chemistry 14