Transcript Nomenclature of coordination compounds: IUPAC rules. Isomerism

Isomerism:
Constitutional isomers,
Stereoisomers.
D-Najlaa alradadi
1
• Isomers
Structural isomer:
same composition, but different
atom connectivity
Stereo isomer:
same atom connectivity, but
Spatial arrangement of different
atoms
D-Najlaa alradadi
2
Molecules that have the same chemical
composition but differ in structural
composition is called isomers
and called this property isomerism
D-Najlaa alradadi
3
Items appear transitional property
isomerism very clearly so we will
talk about the different types of
isomerism
D-Najlaa alradadi
4
isomerism
spatial
Position
Geometric Isomerism
Ionization Isomerism
Hydrate Isomerism
Optical Isomerism
Linkage Isomerism
Monomer Isomerism
Coordination Isomerism
Coordination Position Isomerism
Ligand Isomerism
D-Najlaa alradadi
5
* Isomerism water and Isomerism ion
in the cationic complexes.
* Isomerism Linkage -communicationin ionic and cationic complexes.
* Isomerism monomer in the netural complexes.
D-Najlaa alradadi
6
1) Position (
) Isomerism :
1-1)Ionization Isomerism :
This type of isomerism found in the case of
anion exchange between the metal ion is
associated in the area of ​consistency with the
anion in the domain outside of the overlay.
Example :
]Cr(NH3)5SO4[Br ‚ ]Cr(NH3)5Br[ SO4
]Cr(NH3)5SO4[Br + AgNO3
]Cr(NH3)5Br[SO4 + Ba(NO3)2
]Cr(NH3)5SO4[+ + AgBr
]Cr(NH3)5Br[2+ + BaSO4
D-Najlaa alradadi
7
For example:
pentaaminebromidocobalt(III)sulphate
[Co(NH3)5Br]SO4 is red violet and in solution gives
a precipitate with barium chloride, confirming the
presence of sulphate ion,
while pentaaminesulphatecobalt(III)bromide
[Co(NH3)5SO4]Br is red and tests negative for
sulphate ion in solution, but instead gives a
precipitate of AgBr with silver nitrate.
D-Najlaa alradadi
8
In one example the choloride is
bound to the cobalt and bromide is
the counter ion. In the other
coordination isomer the bromide is
coordinated to the cobalt and
chloride is the counter ion.
D-Najlaa alradadi
9
1-2)Hydrate Isomerism :
In complexes where there are a number of water
molecules may have more than one similar
because the water molecule can exist in the
coordination field or found in the crystal lattice,
for example, when we pass hydrogen chloride in a
solution of chrome alum record consists of newly
violet compound ]Cr(H2O)6[Cl3
The nomination of this compound and adding
ether saturated with hydrogen chloride to the
filtrate gives a pale green compound
]Cr(H2O)5Cl[Cl2.H2O
D-Najlaa alradadi
10
While if Reduction hexa oxide chromium by acid
HCl concentration, and left the solution for a
composite consisting ]Cr(H2O)4Cl2[Cl.2H2O
Dark green and solutions of these newly prepared
Similar complexes with silver nitrate to give all,
two-thirds, one third of the existing chloride,
respectively.
D-Najlaa alradadi
11
For example:
[Cr(H2O)6]Cl3 is violet
[Cr(H2O)5Cl]Cl2.H2O is blue-green
[Cr(H2O)4Cl2]Cl.2H2O is dark green.
D-Najlaa alradadi
12
1-3)Linkage Isomerism :
There is this kind of isomerism when the coordination
group contains the two atoms or more can be consistent
with the central atom, such as for example a group (nitrite)
can be linked through the nitrogen atom, known as nitro or
linked through an oxygen atom known as (nitrito) such as :
nitropentaammine Cobalt (III) Chloride
(yellow)
nitritopentaammine Cobalt (III) Chloride
(read)
D-Najlaa alradadi
13
Linkage isomers contain the same ligands but one
or more of the ligands are coordinated to the metal
through a different atoms. These ligands are said
to be bidentate.
D-Najlaa alradadi
14
In other words,
Are compounds that have the same chemical
formula but differ in the type of maize
related to the central atom
(NH4)3]Cr(SCN)6[
)NH4(3]Cr(NCS)6[
D-Najlaa alradadi
15
1-4) Monomer Isomerism :
In the case of neutral complexes
]pt(NH3)2Cl2[n=1
]pt(NH3)4[]ptCl4[n=2
]pt(NH3)3Cl[]ptCl3(NH3)[
Are compounds with the complications of
the values ​of n and have the same atoms in
them.
D-Najlaa alradadi
16
1-5) Coordination Isomerism :
If the complex on the anions and cations
in the same compound, the complex the
isomers differ only in the place of
harmony between the groups, anions
cations. and
or other words, is a compounds with the
same chemical formula but differ in the
quality associated with that is connected to
atom central and usually contains two atoms
in the center .
D-Najlaa alradadi
17
As in the following examples :
[Co( NH3 )6 ]3[Cr (C2O4 )3 ]3 & [Cr ( NH3 )6 ][Co(C2O4 )3 ]
[Cr ( NH 3 ) 6 ][Co( NCS ) 6 ] & [Cr ( NH 3 ) 4 ( NCS ) 2 ][Co( NH 3 ) 2 ( NCS ) 4 ]
[Co( NH3 )6 ][Cr (CN )6 ] & [Co(CN )6 ][Cr ( NH 3 )6 ]
3
3
[Cr ( NH 3 )6 ] [Co (CN )6 ]
3
3
[Co ( NH 3 )6 ] [Cr (CN )6 ]
D-Najlaa alradadi
18
this occurs when both positive and
negative ions of a salt are complex ions
and the two isomers differ in the
distribution of ligands between the
cation
and
anion.
Forthe
example:
[Co(NH3)6][Cr(CN)6]
and
[Cr(NH3)6][Co(CN)6]
D-Najlaa alradadi
19
1-6) Coordination Position Isomerism :
Is a complexes have the same
chemical formula but differ in the
number of ligands that connect to
each central atom where the
substitution between them.
D-Najlaa alradadi
20
Example :
D-Najlaa alradadi
21
1-7) Ligand Isomerism :
Arises from the presence of the same form inside
ligand .
[Co(en) 2 (C6 H 4CH 3 NH 2 )]Cl3
Example :
D-Najlaa alradadi
22
2-Spatial Isomerism :
2-1)Geometric Isomerism :
In this type of isomerism , the coordination groups
(ligands) arrange themselves in different places for
the atom central If we take, for example, compound
(M a2 b2) in the installation (Square planar), this
compound have 2 isomers (I), (II) as the following:
D-Najlaa alradadi
23
However, if complex the symbol
[M abcd] means that the coordination of
the four different groups in the same
(Square planar), the installation of this
compound can be found in three different
arrangements which is has three isomers
D-Najlaa alradadi
24
Composition of regular quartet (Tetrahedral)
of the complexes [M a2b2] or [M abcd] can be
found only in a single image and does not have
isomers.
D-Najlaa alradadi
25
cis-trans isomers occurs in
octahedral and square planar
complexes (but not tetrahedral).
D-Najlaa alradadi
26
Elements that are found in complexes
isomers cis - trans is a nickel models,
especially with
(unsymmetrical glyoximes) as in the
following figure:
R = CH3
−
‚ R = CH2C6H5
D-Najlaa alradadi
27
Coordination number 5 :
Trigonal bipyramidal
Square pyramidal
D-Najlaa alradadi
28
Gives more pictures
engineering
at coordination the
different groups
[MA3B2], and there
are three geometric
shapes of this
complexes is as
follows:
D-Najlaa alradadi
29
Gives more geometric pictures at
different ligands [MA3B2]
Axial
Diagonal
D-Najlaa alradadi
30
As an example of complexes that take
installation (regular octahedron) complex the
[CoCl2(NH3)4] which has the composition
[MX4L2] There is tow isomers cis and trans, as
in the following figure:
cis-[CoCl2(NH3)4]+
trans-[CoCl2(NH3)4]+
D-Najlaa alradadi
31
(Cr - Cl) a determination that the
double polar chlorine
electronegativity more of chromium
electrons part. and thus pulls
How can I differentiate between them?
Measurement methods are determined, we find
the polar double that if Trans (outcome = zero),
while cis (outcome = a specific value).
D-Najlaa alradadi
32
complex octahydral of the type [MA3B3] has tow isomers
geometric first is called (facial) or abbreviated (fac) and
like the second is called (meridional) or abbreviated (mer)
in the like first try to list the coordination groups so that
for every set (A) group of the other type (B) which is on
each of the three axes (x, y, z) tow coordination groups
different (a , B) and thus we get the form (a) There are
other arrangement is that there are two sets coordination
groups of the same type on an axis and not the center of (x)
and two sets of the other type on the axis (y).
(mer-)
(meridional) )b(
)fac-(
(facial) )a (
D-Najlaa alradadi
33
Does not remain then only be set (A)
remaining on the tip of the third axis
(z) the coordination group (B) and
thus we get the form (b):
(mer-)
(meridional) )b(
)fac-(
(facial) )a (
D-Najlaa alradadi
34
Examples of this type of complexes
Gelesinat triple chrome )Ш(
)fac-(
(mer-)
D-Najlaa alradadi
35
fac-[CoCl3(NH3)3]
mer-[CoCl3(NH3)3]
D-Najlaa alradadi
36
2-2)Optical Isomerism :
[CoCl2(en)2]+
dichiorobis(ethylenediamine)Cobalt(III)
This has complex tow isomers (cis) ,(trans) .
)form - cis(
Active optical
)d - form(
)form - trans(
Not Active optical
)l - form(
D-Najlaa alradadi
37
To know is there for them or one similar
to light or not?
We have to draw a mirror image of each.
The next step is to try to put the image of the
original shape of the mirror is clear that the
Trans-like applies to the mirror image-like
while (cis) does not apply to his mirror image.
D-Najlaa alradadi
38
If you like Trans have a molecule level of
symmetry or center of symmetry in the sense
that if you put a mirror perpendicular to the
line or association (Cl - Cl), it divides the
molecule into two halves, each a mirror of the
last words located at the same level of mirror
Dividing into halves are identical or if we we
dropped a column of the chlorine atom at xy))
then extended the line to be an equal distance
to find the same atom of any atom of chlorine
in the other side of the level in this case, the
molecule ion or similar and then apply the
original image on the mirror image .
D-Najlaa alradadi
39
Like (cis) therefore not similar if started from
the chlorine atom, which on the axis (z) and
brought down the column at (xy) and continued
the line to a distance equal level of chlorine
will not find another. atom
the like (cis) rotates the plane of polarized light to
the right is called (d, dextro) runs the mirror
image plane of polarized light to the left and the
so-called (L, levo)
D-Najlaa alradadi
40
Like (cis) and his mirror image, called
together a double optical (enantiomeric paie)
ionic complexes [CoCl2(en)2]+, there has tow
geometrical isomers one rotates the plane of
polarized light and therefore has a similar
light, there is complex of the three isomers.
)form - cis(
)form - trans(
D-Najlaa alradadi
41
The study of ion composition shows
that, despite that this ion has no
geometric isomers, but it can be found
in the two images (a) and (b) as follows
because it lacks the level of parity.
isomer)a(
mirror
isomer)b(
D-Najlaa alradadi
42
Optical isomerism occurs
when a molecule is not
superimposable with its
mirror image.
D-Najlaa alradadi
43
The symbol Λ (lambda):
is used as a prefix to describe the lefthanded propeller twist formed by three
bidentate ligands, as shown.
Likewise, the symbol Δ (delta):
is used as a prefix for the right-handed
propeller twist.
D-Najlaa alradadi
44
Δ-[Fe(ox)3]3−
Λ-[Fe(ox)3]3−
D-Najlaa alradadi
45
Δ-cis-[CoCl2(en)2]+
Λ-cis-[CoCl2(en)2]+
D-Najlaa alradadi
46
(i) cis-isomers of octahedral complexes with
2 bidentate ligands and 2 monodentate ligands
(cis-bis chelates).
D-Najlaa alradadi
47
.
(ii) octahedral complexes with
3 bidentate ligands
(tris chelates)
D-Najlaa alradadi
48
1- Optical symmetry is achieved
provided that apply to two photos on
each other any deviation occurs for
light polarized to the right or left .
2- There is no symmetry of the optical
image of engineering Trans.
If the complex on three ligands bidentate ,
such as [Co(en)3]3+ in this case resides in
the image of overlapping geometric one,
but have a similar light.
D-Najlaa alradadi
49
* What kind of similarity between each pair of the
following compounds?
]COCl(H2O)(en)2[Cl2 and
]ptCL2(NH3)4[ Br2 and
]CO(NH3)5SCN[)NO3(2 and
]COCl2(en)2[Cl.H2O
]ptBr2(NH3)4[Cl2
]CO(NH3)5NCS[(NO3)2
* Determined using the methods of measuring the
polar dual how you can differentiate between the two
forms of Cis and Trans complex [Co(en)2Br2]Cl ?
* Draw all isomers possible for the following complexes?
[Ni(NH3)(H2O)2Br2]
[Cr(NH3)4Cl2]+
* What are the different methods used to differentiate
between the two forms of Cis and Trans complex
[Co(en)2Cl2]+ ?
D-Najlaa alradadi
50