CEM311 - Homework 6

due Friday, April 1 (beginning of the class)

1. Draw the structures of the following ligands, highlight the donor atoms and give the
likely mode of bonding (e.g. monodentate): (a) bpy; (b) [CN]- (c) [ox]2- and (d) PMe3.

a) There are different isomers of bpy (bipyridine). The most common is 2,2--
bipyridine which is a bidentate ligand (the donor atoms are shown in red)

N N
b) The cyanide ion is generally a monodentate ligand which binds metals
from the carbon side; binding from the nitrogen side can also sometime
occur, although this is rare with inorganic metals. This ligand is also
known to sometime serve as a bridge between two different metal ions,
binding one metal with carbon and the other metal with the nitrogen side.

c) Oxalate is a bidentate ligand; it cannot bind from all four oxygens on a

single metal at the same time because of its planar geometry; like CN-
though, it could bridge two different metal ions.

O O

O O
d) Trimethylphosphine is monodentate

P CH3
H 3C CH3

2. Sketch all stereoisomers of a) [Ru(OH2)4(NH3)2]2+, b) [Ru(OH2)3(NH3)3]2+, and

[Ru(OH2)2(NH3)2(en)]2+. Label all structures and indicate if they are chiral.

a) There are two stereoisomers: cis-[Ru(OH2)4(NH3)2]2+ and trans-[Ru(OH2)4(NH3)2]2+

b) There are two stereoisomers fac-[Ru(OH2)3(NH3)3]2+ and mer-[Ru(OH2)3(NH3)3]2+

c) There are four isomers:

Trans,cis-[Ru(OH2)2(NH3)2en]2+ and cis,trans-[ Ru(OH2)2(NH3)2en]2+
And two optical isomers (which are chiral) of cis,cis-[ Ru(OH2)2(NH3)2en]2+
3. Draw the d-orbital crystal field splitting diagram for [Cr(OH2)6]3+. [CrF6]3- is green and
[Cr(NH3)6]3+ is yellow. What color do you think [Cr(OH2)6]3+ is? Explain your answer.

2 2 2
z x -y

xz yz xy
These are all d3 octahedral complexes, with increasing field strength from F- to
H2O to NH3. [CrF6]3- is green meaning it absorbs low energy red light, [Cr(NH3)6]3+
is yellow so it absorbs higher energy violet light (consistent with stronger field). The
aquo ligand is between fluoride (F--) and ammine (NH3) ligands in the
spectrochemical series; [Cr(OH2)6]3+ would logically absorb light of intermediate
energy between red and violet (that is, about yellow), which would give it a violet
color.

4. (a) Which of the following complexes would you expect to suffer from a Jahn-Teller
distortion: [CrI6]4-, [Cr(CN)6]4-, [CoF6]3-, and [Mn(ox)3]3-? Give reasons for your
answers.

[CrI6]4-, This is a weak field, high spin, d4 Cr(II) complex. 1 electron in degenerate
eg (antibonding) orbitals would result in a strong J-T distortion.

[Cr(CN)6]4-, This is a strong field, low spin, d4 Cr(II) complex. This results in
degenerate electronic configuration in non-bonding orbitals, so this would result
in a weak J-T distortion.

[CoF6]3-, This is a d6 Co(III) complex. You have to decide if it is high or low spin.
F- is a very weak field ligand and cobalt is first row metal, which point to high
spin, but the relatively high oxidation state of Co increases the field to make this
a low spin complex with no J-T distortion. Note the Co(II) complex is high spin

[Mn(ox)3]3- This is a d4 Mn(III) complex. All d4 Oh complexes are electronically

degenerate, which results in J-T distortions.

5. Discuss the following observation:(a) The [CoCl4]2- ion is a regular tetrahedron, but
[CuCl4]2- has a flattened tetrahedral structure.
 xz yz xy

2 2 2
z x -y
[CoCl4]2- is d7 Co(II) – (not relevant here, but remember that all tetrahedral
complexes are high spin) – which is not electronically degeneration and thus
should not distort and a regular tetrahedron results. [CuCl4]2- is a d9 Cu(II)
complex however, with an unpaired electron in one of the energetically
degenerate T orbitals (xy, xz, or yz), which should result in a J-T distortion, hence
the flattened structure.

6. [Et4N]2[NiBr4] is paramagnetic, but K2[PdBr4] is diamagnetic. Rationalize these

observations.

These are both d8 4-coordinate complexes. The observation that there are unpaired
electrons in NiBr4 is consistent with a tetrahedral structure, whereas the observation
that PdBr4 has no unpaired electrons suggests it must have another structure that
removes the degeneracy of the T2 orbitals – in this case it is square planar.

Additional Optional Practice Problems

1. Which of the following ions are diamagnetic: (a) [Co(OH2)6]3+ (b) [CoF6]3- (c) [NiF6]2-
(d) [Fe(CN)6]3- (e) [Fe(CN)6]4- (f) [Mn(OH2)6]2+? Rationalize your answer.

2. (a) Explain why there is no distinction between low- and high-spin arrangements for
an octahedral d8 metal ion.
(b) Discuss the factors that contribute to the preference for forming either a high- or a
low-spin d4 complex.
(c) How would you distinguish experimentally between the two configurations in (b)?

3. For which member of the following pairs of complexes would Δo be the larger and
why:
a) [Cr(OH2)6]2+ and [Cr(OH2)6]3+
b) [CrF6]3- and [Cr(NH3)6]3+
c) [Fe(CN)6]4- and [Fe(CN)6]3-
d) [Ni(OH2)6]3+ and [Ni(en)3]2+
e) [MnF6]2- and [ReF6]2-
f) [Co(en)3]3+ and [Rh(en)3]3+