Catalysis − B(C6 F5 )3 is a co-catalyst which acts as an alkyl abstracting agent to activate the

catalyst and form a cationic complex with a vacant site (or weakly bound substrate –
Group 4 metallocene catalysts like 1 are frequently used as catalysts in Ziegler-Natta
polymerisation.
e.g. solvent)
− This cationic complex formed is now coordinatively unsaturated which means that
ethene can bind and insert itself into the Ti-Me bond to propagate the polymer chain
which eventually ends with chain termination

e) In light of your answer to part d) draw a catalytic cycle for the polymerisation of ethylene
by 1 with B(C 6 F5 )3 . Give the oxidation state and the d-electron count at every step. (3 marks)

a) Give the oxidation state, d-electron count and total valence electron count of 1. (1 mark)
− Oxidation state: Cp: -1; Me = -1; Ti = +4
− d n : 4 – 4 = d0
− Valence e-:
o 2 x Cp = 2 x 5 = 10
o 2 x Me = 2 x 1 = 2
o Ti = 4
o 10 + 2 + 4 = 16 e-

b) Predict and give an annotated sketch of the 1 H NMR of 1. You may assume all nuclei other −
than 1 H are NMR inactive. (2 marks)
f) Compound 2, when combined with B(C 6 F5 )3 , is often used in the polymerisation of
propene. What differences might you expect in the propene polymerisation products when 2
or 1 are used as catalysts? Show your reasoning. (5 marks)

−
− When propene is polymerised, the stereochemistry of the product needs to be
c) What features (if any) would you expect to see in the UV-Vis spectrum of 1. (1 mark) considered. The ordering of the orientation of the methyl groups will result in
− As 1 is d0 , there will not be any d-d transition (no d-electrons which means no metal significantly different products.
ligand charge transfer (MLCT))
− However, ligand metal charge transfer would be seen as Cp ligand has p-electrons

d) Explain the following observations:

Observation 1: When 1 is combined with ethene alone no polymerisation occurs − (refer to MM)
Observation 2: When 1 is combined with ethene in the presence of a Lewis acid such as
− 1: no steric preference -> atactic (random distribution of Me)
B(C6 F5 )3 polymerisation occurs rapidly.
− Observation 1:
− Ethene does not react with complex 1 as it is coordinatively saturated and hence,
ethene cannot bind to initiate polymerisation −
− Observation 2: − 2: sterics -> Me group points away from ring -> syndotactic
 −

Give three methods to identify the rate-determining step in a catalytic process. (3 marks)
− Computational modelling/density functional theory
− Identification of components in the rate equation
− Kinetic isotope effect

Predict the outcome for of the following catalytic reactions. In each case explain any
selectivity and draw the catalytic cycle. You may abbreviate the catalyst in catalytic cycles as
[M].

a)

b)
(4 marks)

(4 marks)

− −

c)

(4 marks)
 The reaction below can be catalysed by [Ni(PPh 3 )2 ]. The catalytic cycle for this is shown
below.

Intermediate D is the resting state of the catalyst and shows no hydridic resonances in the 1 H
NMR.

a) For intermediates A-E give structures and total valence electron counts of the Ni centres.
(10 marks)
− − A:

d)

−
(4 marks) − Valence e-:
o 1 x Ni = 10
o 2 x PPh3 = 2 x 2 = 4
o 1 x C2 H4 = 2
o 10 + 4 + 2 = 16 e-
− − A -> B (+ HCN) – oxidative addition
− B:

−
− Valence e-:
o 1 x Ni = 10
o 2 x PPh3 = 2 x 2 = 4
o 1 x C2 H4 = 2
o 1 x CN = 1
o 1xH=1
o 10 + 4 + 2 + 1 + 1 = 18 e-
− B -> C (-PPh3 ) – ligand dissociation
− C:

−
 constant an order of magnitude greater than the other two. Explain these observations. [NMR
nuclei: 13 C (I = 1/2, assume only present in H 13 CN); 31 P (I = 1/2, 100%)] (3 marks)
− Intermediate D:

−
− Valence e-:
o 1 x Ni = 10 −
o 1 x PPh3 = 2 − Isomers:
o 1 x C2 H4 = 2
o 1 x CN = 1
o 1xH=1
o 10 + 2 + 2 + 1 + 1 = 16 e-
−
− C -> D (+ C2 H4 ) – substitution − 31 P{1 H}NMR would couple most strongly to trans due to the trans effect (furthest
− D: right isomer -> coupling constant an order of magnitude than the two other cis
− 2 JP-C = 2nI + 1 = 2(1)(1/2) + 1 = 2 -> doublet

δ[B]
d) The rate law for this catalytic cycle is: = k[Ni(PPh3 )2 ][PPh3 ]. Qualitatively explain
δt
this rate law. (2 marks)
−
− Valence e-: − Rate law depends on the concentration of catalyst and the concentration of phosphine
o 1 x Ni = 10 − Given that D is the resting state the equilibrium to E must lie towards D, therefore a
o 1 x PPh3 = 2 higher concentration of phosphine will push this equilibrium towards E
o 1 x C2 H4 = 2
o 1 x CH 3 CH2 = 1 e) At -40°C; k = 0.92 x 10-3 L mol-1 s-1 . Find ΔG‡ (in kJ mol-1 ). (1 mark)
ΔG ‡
o 1 x CN = 1 k T −( RT )
− k= B e
o 10 + 2 + 2 + 1 + 1 = 16 e- h
− D -> E (+PPh3 ) – ligand association o k - 0.92 x 10-3 L mol-1 s-1
o kB - 1.381 x 10-23 J K-1
− E:
o T - -40 + 273.15 = 233.15 K
o h - 6.626 x 10−34 Js
o R - 8.314 J mol-1 K-1
ΔG ‡
(1.381 x 10 −23 ) x 233 .15 −( )
− 0.92 x 10−3 = e 8.314 x 233 .15
6.626 x 10 −34
− − ΔG‡ = 70176.3438… J mol-1 = 70.1763… kJ mol-1 = 70.2 kJ mol-1 (3 s.f.)
− Valence e-:
o 1 x Ni = 10 f) Given that ΔH ‡ = 36.8 kJ mol-1 find ΔS‡ . Use your answer from d) to rationalise the sign
o 2 x PPh3 = 2 x 2 = 4 of ΔS‡ . (in kJ mol-1 K -1 ). (2 marks)
o 1 x C2 H4 = 2 − ΔG‡ = ΔH‡ – TΔS‡
o 1 x CH 3 CH2 = 1 o ΔG‡ - 70176.3438… J mol-1
o 1 x CN = 1 o ΔH‡ - 36.8 kJ = 36800 J
o 10 + 4 + 2 + 1 + 1 = 18 e- o T - -40 + 273.15 = 233.15 K
− 70176.3438… = 36800 – (233.15)ΔS‡
b) Explain the geometry of intermediate C. (2 marks) − ΔS‡ = -143.1539… J mol-1 K-1 = -0.14315… kJ mol-1 K -1 = -0.143 kJ mol-1 K-1 (3 s.f.)
− Oxidation state of Ni = +2
− dn : 10 – 2 = d8 -> square planar is preferred Hydroformylation is the formal addition of CO and H 2 to an alkene:
− ligands CN and PPh3 are high field ligands

c) The 31 P{1 H} NMR spectrum of intermediate D displays three singlet resonances. When
H13 CN is used these resonances all become doublets with one resonance having a coupling
It can be catalysed by Co2 (CO)8 . This is called the ‘oxo-process’.
a) Give the structure, total valence electron count, d electron count and oxidation state of
Co2 (CO)8 .

−
− 1 x Co = 1 x 9 = 9
− 4 x CO = 4 x 2 = 8
− 1 x Co-Co = 1
− e- count: 9 + 8 + 1 = 18 e-

−
− 1 x Co = 1 x 9 = 9
− 3 x CO (L) = 3 x 2 = 6
− 2 x CO (X - bridge) = 2 x 1 = 2
− 1 x Co-Co = 1
− e- count: 9 + 6 + 2 + 1 = 18 e-

b) Suggest a catalytic cycle. For every intermediate give the d-electron count, total valence
electron count and the oxidation state of Co.

−
− A:
o From a)
− B:
o 1 x Co = 1 x 9 = 9
o 4 x CO = 4 x 2 = 8
o 1xH=1
o e- count: 9 + 8 + 1 = 18 e-
o Oxidation: CO = 0; H = -1; Co = +1
o dn : 9 – 1 = d8
− C:
o 1 x Co = 1 x 9 = 9
o 3 x CO = 3 x 2 = 6
o 1xH=1
o e- count: 9 + 6 + 1 = 16 e-
o Oxidation: CO = 0; H = -1; Co = +1
 o dn : 9 – 1 = d8
− D:
o 1 x Co = 1 x 9 = 9
o 3 x CO = 3 x 2 = 6 −
o 1xH=1 − E -> F: + CO – ligand association
o 1 x CH 2 =CH-R = 2 − F -> G: migratory insertion
o e- count: 9 + 6 + 1 + 2 = 18 e-
o Oxidation: CO = 0; H = -1; CH 2 =CH-R = 0; Co = +1
o dn : 9 – 1 = d8
− E:
o 1 x Co = 1 x 9 = 9 −
− G -> H: +H 2 – oxidative addition
o 3 x CO = 3 x 2 = 6
o 1 x RCH 2 CH2 - = 1 − Likely concerted
o e- count: 9 + 6 + 1 = 16 e- − H -> A: - RCH2 CH 2 COH – reductive elimination
o Oxidation: CO = 0; RCH 2 CH2 - = -1; Co = +1 − concerted
o dn : 9 – 1 = d8
− F: d) How would you probe your catalytic cycle? What would you expect to see?
o 1 x Co = 1 x 9 = 9 − IR spectroscopy - highly sensitive for detecting intermediate species in a catalytic
o 4 x CO = 4 x 2 = 8 cycle
o 1 x RCH 2 CH2 - = 1 − By monitoring the IR spectrum, characteristic vibrational stretches of intermediates
o e- count: 9 + 8 + 1 = 18 e- can be observed
o Oxidation: CO = 0; RCH 2 CH2 - = -1; Co = +1 − Raman Spectroscopy - similar to IR spectroscopy, it can be utilised to examine the
o dn : 9 – 1 = d8 vibrations of intermediates
− G: − Offers information for probing specific modes of vibrations that might not be easily
o 1 x Co = 1 x 9 = 9 detected by IR spectroscopy
o 3 x CO = 3 x 2 = 6 − Measurement of rates with changing pressures - by varying the pressure of reactants
o 1 x RCH 2 CH2 CO- = 1 (eg. CO andH 2 ) the rate of catalytic reactions can be measured
o e- count: 9 + 6 + 1 = 16 e- − Provides information about the dependence of the reaction rate on the concentration
o Oxidation: CO = 0; RCH 2 CH2 CO- = -1; Co = +1 of these reactants, which can give insights into the catalytic cycle and the rate-
o dn : 9 – 1 = d8 determining steps
− H: − Measurement of rates with changing concentrations - by altering the concentration of
o 1 x Co = 1 x 9 = 9 reactants, specifically the alkene in this case, the rate of the catalytic reaction can be
o 3 x CO = 3 x 2 = 6 determined
o 1 x RCH 2 CH2 CO- = 1 − helps to understand the relationship between the concentration of the alkene and the
o 2xH=2x1=2 rate of the catalytic cycle
o e- count: 9 + 6 + 1 + 2 = 18 e- − Deuterium labelling/kinetic isotope effect (KIE – used to investigate the reaction
o Oxidation: CO = 0; RCH 2 CH2 CO- = -1; H = -1 Co = +3 mechanism and identify the rate-determining steps
o dn : 9 – 3 = d6 − By replacing 1 H atoms with 2 D atoms in specific positions, the impact on reaction
rates can be measured -> provides insights into the bond-breaking and bond-forming
c) Give a name for every transformation within your catalytic cycle and propose (where processes within the catalytic cycle
applicable) a mechanism for the transformation (There is an activation process for the − 13 C labelling - 13 C labelling can provide some information about the reaction
catalyst featuring two steps. The first step of which is a bimetallic oxidative addition to give mechanism but it is generally less pronounced for carbon isotopes as it is highly
Co(CO)4 H). unlikely that the C-O bond would be fully cleaved, making 13 C labelling less
− A -> B: + H 2 – oxidative addition informative than 2 D labelling
− B -> C: -CO – ligand dissociation
− C -> D: +L – ligand association Provide a retrosynthetic analysis to show how compound A could be synthesised from acyclic
− D -> E: migratory insertion starting materials. Give reagents for the forward synthesis, which should include a catalytic
carbon-carbon bond forming reaction.
 −
− Ring closing metathesis -> Grubb’s catalyst is used

The 1,2-diol below was required as the diastereomer shown. Give a retrosynthetic analysis
for this diol involving an alkene difunctionalisation and a carbonyl olefination reaction. Give
reagents for the forward synthesis.

Compound C is an intermediate in a total synthesis of the anti-fungal natural product

pterulone. Compound C was synthesised from B in 4 steps. Give the structure of the product
from each step, explaining any selectivity observed. Suggest a reagent that could be used to
effect step 4.

Show a retrosynthetic analysis that provides a synthetic route for the target molecule below
from an acyclic precursor. How might you synthesise the acyclic precursor?
− Step 1:

−
− Phenolic proton (H) is most acidic -> removed by base
− Step 2:

Lapatinb (Tykerb, GSK) is a drug used to treat breast cancer and other solid tumours. The
−
late-stage precursor A was synthesised using a Suzuki coupling. Which bond in A would you
− Wittig reaction -> works on aldehyde > ketone
disconnect, and what would be the coupling partners?
− Step 3:

−
− Standard protection of the ketone as cyclic acetal
− Step 4:
 −

Give a retrosynthetic analysis using a cross-coupling reaction, to develop a stereocontrolled

synthesis of the target molecule below.