CHE-6301Y Inorganic Molecules: Structure and Function Summative Coursework 1

Q1) Complex 1 catalyses the metathesis of alkenes but much more slowly than complex 2. With
reference to the appropriate step(s) in the mechanism explain why this is the case.

N N

Figure 2: 1,3-Bis(2,4,6-
trimethylphenyl)imidazol-2-ylidene
(N-heterocyclic carbine)

Figure 1: PCy3

Both of complex ones present ligands are N-heterocyclic carbenes (NHC) which form very strong
bonds with the metal complex for which they are bonded to. This makes it very hard to dissociate
during metathesis. This compared with complex 2 shows us why complex 2 is the preferred catalyst.
PCy3, the ligand present in complex 2, is a weak base with a pK a of 9.7. Weak bases make for good
leaving groups due to their ability to accept electrons. The PCy 3 ligand also has a large cone angle of
170o making it a sterically bulky ligand. This makes the ligand a good leaving group. PCy 3 is also more
stable than the N-heterocyclic carbene as a free ligand. In terms of bonding the PCy 3 ligand forms
weaker pi and sigma bonds than the NHC meaning that it forms stronger bonds in the complex and
thus stabilises the complex better than PCy 3

Q2) The di-iron complex 3 will react with protons to give 4 and can then be reduced by a strong
electron donor to yield 5.

Calculate electron counts and assign oxidation states for the iron atoms in 3 and 4; show how you
reach your conclusions.

Compound 3 has an electron count of 18 for each iron with n oxidation state of 2+ the workings for
electron counting can be seen bellow:

4 X CO = 8

2 X PMe3 = 4

SCH2CH2S = 6

2 X Fe = 16

Metal-metal bond = 2

36 ÷ 2 = 18
We see an electron count of 6 for the sulphur due each sulphur contributing 3 electrons one to a
shard electron bond with iron and the other 2 from a dative bond with the other iron. We see an
oxidation state of 1+ because each sulphur atom has a charge of 1 -

Compound 4 has an electron count of 17 and an oxidation state of 1+. The workings for the electron
count for complex 4 are the same as 3. However, we do not see the shared electron present in the
metal-metal bond. This is because instead of the meal-metal bond a proton has been bonded

Complex 5 has radical character. What are the electron count(s) and oxidation state(s) for the two
iron atoms in this complex?

The electron count for complex 5 is the same as the electron count of complex 4. However, due to
the presence of the radical one of the iron atoms has a count of 18 and the other has a count of 17.
The oxidation state is still 1+ because radicals do not affect the oxidation state of a complex.

Q3) The complex TiMe4 is an reactive liquid which can be handled at using air-sensitive
techniques. In contrast, other TiR4 compounds (R = linear alkyl group) are not isolable.

Explain this observation

TiR4 groups, where the R is a linear alkyl group, will undergo β hydride elimination with alkene
formation causing the compound to decompose.

Would you expect Ti(CH2CMe3 )4 to be isolable? Justify your answer.

Yes. Due to the separation of the t-Bu group from the titanium atom, with a CH 2 group, there are no
hydrogens present on the β carbon. The molecule itself is stable to 105 oc

Q4) The substitution reaction of CpRe(CO)3 with PMe3 Re OC CO CO Re Me3P CO CO PMe3 6 7 has
rate equation − d[CpRe(CO)3 ] / dt = k[CpRe(CO)3 ][PMe3 ]

State whether the reaction is associative or dissociative.

Associative

Suggest a mechanism for the reaction?

Re Re Re
CO CO CO
OC OC Me3P
CO Me3P CO CO