Exercise: How many stereoisomers does an octahedral complex ...
Exercise: How many stereoisomers does an octahedral complex ...
Exercise: How many stereoisomers does an octahedral complex ...
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Isomerism in Octahedral Tr<strong>an</strong>sition Metal Complexes <br />
As you have seen in the chemistry of carbon‐containing compounds, often there are several isomers <br />
possible for the same compound formula. Even when atoms are connected in the same order it is <br />
possible that we have not uniquely described the structure of the molecule. For example, because there <br />
is no free rotation about a double bond, the cis <strong>an</strong>d tr<strong>an</strong>s isomers are separate entities with different <br />
properties. This type of isomerism is referred to as disasteromerism (or geometric isomerism or cistr<strong>an</strong>s isomerism). Alternatively , if the four groups surrounding a tetrahedral atom are not the same, the <br />
molecule is not superimposable on its mirror image. Molecules not superimposable on their mirror <br />
images are called en<strong>an</strong>tiomers (or optical isomers). <br />
Because carbon obeys the octet rule, there are at most four different groups <strong>an</strong>d two en<strong>an</strong>tiomers <br />
possible per tetrahedral carbon. But what happens when there are more th<strong>an</strong> four groups around a <br />
central atom This commonly happens in tr<strong>an</strong>sition metal chemistry where there are often six groups <br />
(called lig<strong>an</strong>ds) around a central metal atom. [ In fact, if there are six different groups in <strong>an</strong> <strong>octahedral</strong> <br />
arr<strong>an</strong>gement around a metal atom, there are 15 different geometric isomers, <strong>an</strong>d each one exists as a <br />
pair of en<strong>an</strong>tiomers, for a total of thirty <strong>stereoisomers</strong>!] This activity will introduce you to a systematic <br />
way to determine the number of geometric <strong>an</strong>d optical isomers in <strong>an</strong> <strong>octahedral</strong> tr<strong>an</strong>sition metal <br />
<strong>complex</strong>. <br />
Before you begin, you should be familiar with the common lig<strong>an</strong>ds that c<strong>an</strong> connect to a tr<strong>an</strong>sition <br />
metal. There is such a list on page 825 of your textbook. Note that <strong>m<strong>an</strong>y</strong> donate one pair of electrons <br />
(monodentate lig<strong>an</strong>ds) while others donate two pairs of electrons (from different atoms in the lig<strong>an</strong>d). <br />
The latter are called bidentate lig<strong>an</strong>ds. In <strong>an</strong> <strong>octahedral</strong> <strong>complex</strong> there are a total of six pairs of <br />
electrons around the metal ion. These pairs c<strong>an</strong> come from six monodentate lig<strong>an</strong>ds, three bidentate <br />
lig<strong>an</strong>ds, a bidentate lig<strong>an</strong>d <strong>an</strong>d four monodentate lig<strong>an</strong>ds, or <strong>an</strong>y other combination that you c<strong>an</strong> think <br />
of. By knowing the names <strong>an</strong>d abbreviations of the lig<strong>an</strong>ds you c<strong>an</strong> determine number of electron pairs <br />
around the metal ion. <br />
Let’s do <strong>an</strong> example. Determine the number of geometric <strong>an</strong>d optical isomers of [Co(NH 3 ) 3 BrClF]. <br />
<br />
Quick check—we have six monodentate lig<strong>an</strong>ds attached to the cobalt, so this should be <strong>an</strong> <strong>octahedral</strong> <br />
<strong>complex</strong>. <br />
<br />
1. Draw one isomer. (It <strong>does</strong>n’t matter which one.) In this case we <br />
c<strong>an</strong> abbreviate the lig<strong>an</strong>d names further, as long as doing so <br />
<strong>does</strong>n’t create confusion—for example NH3 =N. <br />
2. Lig<strong>an</strong>ds that are 180 o to each other are said to be tr<strong>an</strong>s. <br />
Describe the isomer by writing tr<strong>an</strong>s pairs in parentheses. Thus, <br />
the structure drawn here is (Br, N), (Cl, F), (N, N). Each <br />
geometric isomer will have a unique combination of tr<strong>an</strong>s lig<strong>an</strong>ds. You c<strong>an</strong> avoid confusion by <br />
alphabetizing lig<strong>an</strong>ds both within the parentheses <strong>an</strong>d among the set of three tr<strong>an</strong>s pairs. If you <br />
do this, it allows you to easily recognize whether <strong>an</strong>other structure is just <strong>an</strong>other picture of <br />
what you have already drawn or a unique isomer. <br />
<br />
Example‐ Does the following represent a new geometric isomer of the <strong>complex</strong>: <br />
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3. Lig<strong>an</strong>ds that are 90 o to each other are said to be cis. Now try switching a pair of cis lig<strong>an</strong>ds <strong>an</strong>d <br />
drawing the picture. (You c<strong>an</strong> avoid drawing repeat structures if you switch just two lig<strong>an</strong>ds at a <br />
time rather th<strong>an</strong> r<strong>an</strong>domly drawing a new structure.) Use the method for describing the <br />
<strong>complex</strong>’s lig<strong>an</strong>ds as given in #2. Is it the same isomer as one you already have Continue this <br />
process until you c<strong>an</strong>’t generate <strong>an</strong>y new structures. <br />
Example—draw all of the remaining geometric isomers for [Co(NH 3 ) 3 BrClF]. Under each one that you <br />
draw, list the lig<strong>an</strong>ds in tr<strong>an</strong>s pairs as described above. (Hint—there are a total of four, including the <br />
first one already shown.) <br />
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<br />
<br />
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4. If the <strong>complex</strong> contains a bidentate lig<strong>an</strong>d, the ends of that lig<strong>an</strong>d must occupy cis sites around <br />
the octahedron. (For all common lig<strong>an</strong>ds, the chain of atoms connecting the atoms attached to <br />
the metal ion is not long enough for the atoms in the same bidentate lig<strong>an</strong>d to be across from <br />
each other.) Connect the atoms in a bidentate lig<strong>an</strong>d with a line. <br />
Thus, en= .
<br />
5. For each geometric isomer, there is the possibility that its mirror image is non‐superimposable. <br />
If so, that isomer exists as a pair of en<strong>an</strong>tiomers. There are two ways of determining this. First, <br />
you could build a model of the isomer, build its mirror image, <strong>an</strong>d then attempt to lay the two <br />
models on top of each other. If you c<strong>an</strong> get all of the atoms to align, the mirror image is <br />
superimposable <strong>an</strong>d you just have two copies of the same thing. If you c<strong>an</strong>’t get them to align, <br />
then the two structures are en<strong>an</strong>tiomers <strong>an</strong>d represent different ways of arr<strong>an</strong>ging the atoms. <br />
The second method is really just a variation on the first but <strong>does</strong> not involve building models. In <br />
this case, look for a mirror pl<strong>an</strong>e within the molecule. If there is a pl<strong>an</strong>e within the molecule <br />
such that one half of the molecule is identical to the other half, then the mirror image WILL be <br />
superimposable on the original. If there are no such pl<strong>an</strong>es then the structure will exist as a pair <br />
of en<strong>an</strong>tiomers. There are several “trial” pl<strong>an</strong>es that we might look at. Three are shown below. <br />
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In the first one, the pl<strong>an</strong>e contains two tr<strong>an</strong>s N’s, the Cl <strong>an</strong>d the F. (All pl<strong>an</strong>es must also contain the <br />
central atom.) Any atom that is in the selected pl<strong>an</strong>e reflects into itself. Note that the Br <strong>an</strong>d one of the <br />
N’s are outside of the pl<strong>an</strong>e. If this represented a pl<strong>an</strong>e of symmetry within the molecule, the reflection <br />
of the Br would have to be <strong>an</strong>other Br. Since there is <strong>an</strong> N on the opposite side of the mirror from the <br />
Br, this site <strong>does</strong> not represent a mirror pl<strong>an</strong>e of symmetry within the structure. So, let’s look at the <br />
second picture. In this case a mirror pl<strong>an</strong>e containing N, F Br <strong>an</strong>d Cl is shown (perpendicular to the pl<strong>an</strong>e <br />
of the paper). This reflects <strong>an</strong> N into <strong>an</strong>other, so there is a mirror pl<strong>an</strong>e of symmetry in this location. In <br />
the third picture, a mirror pl<strong>an</strong>e is showing passing between the Br <strong>an</strong>d Cl, <strong>an</strong> N <strong>an</strong>d <strong>an</strong> F <strong>an</strong>d containing <br />
the other two N’s (this is the pl<strong>an</strong>e containing the paper). This pl<strong>an</strong>e would reflect the Br into the Cl <br />
(<strong>an</strong>d the F into the N) so it c<strong>an</strong>not be a symmetry pl<strong>an</strong>e. Because we have found one symmetry pl<strong>an</strong>e <br />
within the molecule, this isomer will be superimposable on its mirror image <strong>an</strong>d thus will not exist as <br />
optical isomers. <br />
Note—when looking for symmetry pl<strong>an</strong>es in molecules containing bidentate lig<strong>an</strong>ds, you must take into <br />
account the part of the molecule that connects the two ends of the bidentate lig<strong>an</strong>d. <br />
Example: Examine the geometric isomers you have drawn for [Co(NH 3 ) 3 BrClF]. For those that have one, <br />
draw a symmetry pl<strong>an</strong>e within the molecule. (Hint—there is one isomer that <strong>does</strong>n’t have a symmetry <br />
pl<strong>an</strong>e.)
Isomerism in Octahedral Tr<strong>an</strong>sition Metal Complexes <br />
Takehome points: (These points are more completely explained earlier.) Carefully read it for complete <br />
expl<strong>an</strong>ation.) To determine the number of possible isomers (geometric <strong>an</strong>d optical) for <strong>an</strong> <strong>octahedral</strong> <br />
tr<strong>an</strong>sition metal <strong>complex</strong>, <br />
1. Draw one isomer with the lig<strong>an</strong>ds arr<strong>an</strong>ged in <strong>an</strong>y convenient way. <br />
2. Write each of the three pairs of tr<strong>an</strong>s lig<strong>an</strong>ds enclosed in a set of parentheses <br />
3. Switch a pair of cis lig<strong>an</strong>ds <strong>an</strong>d describe the new <strong>complex</strong> using the method in #2. If two structures do <br />
not have the same sets of tr<strong>an</strong>s pairs of lig<strong>an</strong>ds, they are geometric isomers. <br />
4. The different ends of bidentate lig<strong>an</strong>ds must occupy cis sites around the octahedron. <br />
5. Examine each geometric isomer for internal mirror pl<strong>an</strong>es. If there are no such mirror pl<strong>an</strong>es, that <br />
geometric isomer will exist as a pair of en<strong>an</strong>tiomers. <br />
<br />
Practice: for each of the following <strong>complex</strong>es, draw all geometric isomers <strong>an</strong>d label them using the <br />
“tr<strong>an</strong>s pair” naming system. Indicate which exist as a pair of en<strong>an</strong>tiomers. <br />
A. [Cr(H 2 O) 3 (OH) 2 Cl] <br />
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B. [M(NH 3 ) 2 Cl 2 F 2 ] <br />
C. [Ni(en)(ox)(H 2 O)(NH 3 )]