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< Br
< S
2
< SCN
< Cl
< NO
3
< N
3
< F
< OH
< C
2
O
4
2
< H
2
O < NCS
< CH
3
CN < py < NH
3
<
en < 2,2'-bipyridine < phen < NO
2
< PPh
3
< CN
< CO
Field Splitting Energies for Some Octahedral (".
Table 23.10 Crystal Field Splitting Energies for Some Octahedral (o)* and Tetrahedral
(t) Transition-Metal Complexes
Octahedral
Complexes
o
(cm
1
)
Octahedral
Complexes
o
(cm
1
)
Tetrahedral
Complexes
t
(cm
1
)
[Ti(H
2
O)
6
]
3+
20,300 [Fe(CN)
6
]
4
32,800 VCl
4
9010
[V(H
2
O)
6
]
2+
12,600 [Fe(CN)
6
]
3
35,000 [CoCl
4
]
2
3300
[V(H
2
O)
6
]
3+
18,900 [CoF
6
]
3
13,000 [CoBr
4
]
2
2900
[CrCl
6
]
3
13,000 [Co(H
2
O)
6
]
2+
9300 [CoI
4
]
2
2700
[Cr(H
2
O)
6
]
2+
13,900 [Co(H
2
O)
6
]
3+
27,000
[Cr(H
2
O)
6
]
3+
17,400 [Co(NH
3
)
6
]
3+
22,900
[Cr(NH
3
)
6
]
3+
21,500 [Co(CN)
6
]
3
34,800
[Cr(CN)
6
]
3
26,600 [Ni(H
2
O)
6
]
2+
8500
Cr(CO)
6
34,150 [Ni(NH
3
)
6
]
2+
10,800
[MnCl
6
]
4
7500 [RhCl
6
]
3
20,400
[Mn(H
2
O)
6
]
2+
8500 [Rh(H
2
O)
6
]
3+
27,000
Octahedral
Complexes
o
(cm
1
)
Octahedral
Complexes
o
(cm
1
)
Tetrahedral
Complexes
t
(cm
1
)
[MnCl
6
]
3
20,000 [Rh(NH
3
)
6
]
3+
34,000
[Mn(H
2
O)
6
]
3+
21,000 [Rh(CN)
6
]
3
45,500
[Fe(H
2
O)
6
]
2+
10,400 [IrCl
6
]
3
25,000
[Fe(H
2
O)
6
]
3+
14,300 [Ir(NH
3
)
6
]
3+
41,000
*Energies obtained by spectroscopic measurements are often given in units of wave numbers (cm
1
);
the wave number is the reciprocal of the wavelength of the corresponding electromagnetic radiation
expressed in centimeters: 1 cm
1
= 11.96 J/mol.
Source of data: Duward F. Shriver, Peter W. Atkins, and Cooper H. Langford, Inorganic
Chemistry, 2nd ed. (New York: W. H. Freeman and Company, 1994).
Colours of Various Example Coordination Complexes
Fe
2+
Fe
3+
Co
2+
Cu
2+
Al
3+
Cr
3+
Hydrated
Ion
[Fe(H
2
O)
6
]
2+
Pale green
Solution
[Fe(H
2
O)
6
]
3+
Yellow/brown
Solution
[Co(H
2
O)
6
]
2+
Pink
Solution
[Cu(H
2
O)
6
]
2+
Blue
Solution
[Al(H
2
O)
6
]
3+
Colourless
Solution
[Cr(H
2
O)
6
]
3+
Green
Solution
OH
, dilute
[Fe(H
2
O)
4
(O
H)
2
]
Dark green
Precipitate
[Fe(H
2
O)
3
(O
H)
3
]
Brown
Precipitate
[Co(H
2
O)
4
(O
H)
2
]
Blue/green
Precipitate
[Cu(H
2
O)
4
(OH)
2
]
Blue
Precipitate
[Al(H
2
O)
3
(O
H)
3
]
White
Precipitate
[Cr(H
2
O)
3
(O
H)
3
]
Green
Precipitate
OH
,
concentrat
ed
[Fe(H
2
O)
4
(O
H)
2
]
Dark green
Precipitate
[Fe(H
2
O)
3
(O
H)
3
]
Brown
Precipitate
[Co(H
2
O)
4
(O
H)
2
]
Blue/green
Precipitate
[Cu(H
2
O)
4
(OH)
2
]
Blue
Precipitate
[Al(OH)
4
]
Colourless
Solution
[Cr(OH)
6
]
3
Green
Solution
NH
3
, dilute
[Fe(H
2
O)
4
(O
H)
2
]
Dark green
Precipitate
[Fe(H
2
O)
3
(O
H)
3
]
Brown
Precipitate
[Co(H
2
O)
4
(O
H)
2
]
Blue/green
Precipitate
[Cu(H
2
O)
4
(OH)
2
]
Blue
Precipitate
[Al(H
2
O)
3
(O
H)
3
]
White
Precipitate
[Cr(H
2
O)
3
(O
H)
3
]
Green
Precipitate
NH
3
,
concentrat
ed
[Fe(H
2
O)
4
(O
H)
2
]
Dark green
Precipitate
[Fe(H
2
O)
3
(O
H)
3
]
Brown
Precipitate
[Co(NH
3
)
6
]
2+
Straw
coloured
Solution
[Cu(NH
3
)
4
(H
2
O)
2
]
2+
Deep blue
Solution
[Al(H
2
O)
3
(O
H)
3
]
White
Precipitate
[Cr(NH
3
)
6
]
3+
Green
Solution
CO
3
2
FeCO
3
Dark green
Precipitate
[Fe(H
2
O)
3
(O
H)
3
]
Brown
Precipitate +
bubbles
CoCO
3
Pink
Precipitate
CuCO
3
Blue/green
Precipitate
Colors of Lanthanide complexes[edit]
Schematic representation of d-level
splitting
In the formation of an octahedral complex, ligands approach the central atom
or ion along the x, y, and z axes. Maximum interference occurs with the dz2
and dx2-y2 orbitals (shown in yellow). The energies of these orbitals are
raised with respect to those of the dxy, dxz, and dyz orbitals (shown in red).
Table 16.5 A Summary of Types of Complexes Formed by First-Row Metal Ions .
Number of d
Electrons Most Common Ion Usual Geometry b Hybrid Orbital Example
0 Sc 3 _ Octahedral d 2 sp 3 Sc(H 2 O) 6 3 _
1 Ti 3 _ Octahedral d 2 sp 3 Ti(H 2 O) 6 3 _
2 V 3 _ Octahedral d 2 sp 3 VF 6 3 _
3 Cr 3 _ Octahedral d 2 sp 3 Cr(NH 3 ) 6 3 _
4 a Mn 3 _ Octahedral (h.s.) sp 3 d 2 Mn(H 2 O) 6 3 _
4 a Mn 3 _ Octahedral (l.s.) d 2 sp 3 Mn(CN) 6 3 _
5 Fe 3 _ Octahedral (h.s.) sp 3 d 2 Fe(H 2 O) 6 3 _
5 Fe 3 _ Octahedral (l.s.) d 2 sp 3 Fe(CN) 6 3 _
5 Fe 3 _ Tetrahedral sp 3 FeCl 4 _
6 Co 3 _ Octahedral (h.s.) sp 3 d 2 CoF 6 3 _
6 Co 3 _ Octahedral (l.s.) d 2 sp 3 Co(H 2 O) 6 3 _
7 Co 2 _ Octahedral (h.s.) sp 3 d 2 Co(H 2 O) 6 2 _
7 Co 2 _ Trigonal bipyramid dsp 3 Co(CN) 5 3 _
7 Co 2 _ Tetrahedral sp 3 CoCl 4 2 _
7 Co 2 _ Square planar dsp 2 Co(CN) 4 2 _
8 Ni 2 _ Tetrahedral sp 3 Ni(NH 3 ) 4 2 _
8 Ni 2 _ Octahedral sp 3 d 2 Ni(NH 3 ) 6 2 _
8 Ni 2 _ Trigonal bipyramid dsp 3 Ni(CN) 5 3 _
8 Ni 2 _ Square base pyramid sp 2 d 2 Ni(CN) 5 3 _
8 Ni 2 _ Square planar dsp 2 Ni(CN) 4 2 _
9 a Cu 2 _ Octahedral sp 3 d 2 CuCl 6 4 _
9 a Cu 2 _ Tetrahedral sp 3 Cu(NH 3 ) 4 2 _
10 Zn 2 _ Octahedral sp 3 d 2 Zn(H 2 O) 6 2 _5 Multiple Choice Questions
1. hexacyanoferrate(II)
a. [Co(NH)]Cl
b. Fe(CN)
c. K [Fe(CN)]
d. Ru(NH)Cl
triethylenediamminemanganese(II)
. Ru(NH)Cl
a. Mn(NHCHCHNH)
b. [Co(NH)Cl]Cl
c. [Fe(en)(NO)]SO
potassium hexacyanoferrate(III)
. K[Fe(CN)]
a. Fe(CN)
b. K[PtCl]
c. K[PtCl]
hexaamminecobalt(II) chloride
. [Co(NH)Cl]Cl
a. [Co(HO)]I
b. [Co(NH)]Cl
c. Ru(NH)Cl
[Cr(NH)NHCHCHNHCl]I
. triamminechloroethylenediamminechromium(III) iodide
a. sodium dicyanobis(oxalato)ferrate(III)
b. triamminebromoplatinum(II) chloride
c. aquatricarbonylplatinum(II) bromide
5 True/False Questions
1. K[PtCl] potassium tetrachloroplatinumate(II)
True False
2. [Co(NH)Cl]Cl pentaamminechlorocobalt(III) chloride
True False
3. [Co(HO)]I hexaaquacobalt(III) iodide
True False
4. [Fe(en)(NO)]SO hexaaquacobalt(III) iodide
True False
5. Ru(NH)Cl pentaamminechlorocobalt(III) chloride
True False
10 Zn 2 _ Tetrahedral sp 3 Zn(NH 3 ) 4 2 _
10 Ag _ Linear sp Ag(NH 3 ) 2 _
Based on CO IR stretching frequencies, the following ligands can be
ranked from best -acceptor to worst:
NO+ > CO > PF3 > RN