Advanced Inorganic Research Practical Report William Hodds

The Effect of Phosphine Ligand Substituent Structure

on the Catalytic Activity of Grubbs-type Catalysts in
the Ring Closing Metathesis of Diethyl Diallylmalonate
William Hodds
kaki

Abstract

In this work, ring closing metathesis (RCM) of diethyl diallylmalonate (DEDAM) was conducted using
two Ru-phenylindenylidene complexes (1st generation Grubbs catalysts) in which only the
triphosphine ligand varies (R = Cy, R = Ph). It is found that the phosphine ligand has a substantial
effect on the catalytic turnover of ring product, by merit of the size and the -donating effect of the
phosphine ligand. It is found that the larger, more -donating PCy3 ligand is more catalytically active
than the corresponding complex with PPh3, as shown by 1H-,13C-NMR and GC-MS analysis. These
results are rationalised by consideration of the Chauvin dissociative RCM mechanism, and add to the
literature-wide consensus first established by Grubbs et al, which is in agreement with the findings
of this study.
KEYWORDS: 1st Generation Grubbs Catalyst, Ring Closing Metathesis, Diethyl Diallylmalonate,
Phosphine Ligands, Catalytic Activity, Ruthenium Phenylindenylidene, Carbene ligand.

Introduction
Ring closing metathesis reactions are important for their use in the synthesis of a wide range of
target molecules, such as macrocyclic Hepatitis C protease inhibitors [1], cyclic polymers [2], and
even in synthetic analogues to peptides, where metabolically-sensitive disulphide bridges may be
replaced with inert carbon-based bridges in order to stabilise the peptide to a point where more
harsh characterisation analyses may be undertaken [3].
With any important reaction, there is ongoing work continuously published in efforts to optimise
1

Advanced Inorganic Research Practical Report William Hodds

reaction conditions and potential catalysts, in order to achieve high yields and rates of reactions,
with great impact on both the economic footprint of the reaction as well as the green footprint.
To date, a number of structurally different Grubbs catalysts are employed in RCM:

a)

b)

c)

Fig 1. Three different Grubbs-type catalysts, a) 1st generation Grubbs catalyst b) 2nd generation
Grubbs catalyst c) 1st generation Hoveyda-Grubbs catalyst.
At once, it can be seen that the bulk of the adjustments made in these complexes are the ligands,
whereas the metal-carbon carbene bond and Ru IV centre being constant features to a successful
Grubbs catalyst. By inspection of the most supported mechanism for RCM, the Chauvin mechanism
[4], it can be seen that the carbene functionality is vital to the catalytic activity of the complex, the
carbene being the participating group while other ligands serve kinetic or thermodynamic stabilising
roles.
The non-participating ligands are by no means unimportant however, as they infer air and water
stability on the complex, as well as some degree of functional group tolerance in the alkene/olefin
substrate [5]. It is this stability that has allowed Grubbs catalyst to become so ubiquitous in organic
synthetic chemistry, and as such, it is a powerful technique to research the effect of these ligands on
the rate of catalytic turnover (or simply % conversion in a specified time frame) and resistance to
degradation. Many efforts have been made with successful insights into the Grubbs catalyst system,
and in this study this ever-growing foundation of knowledge is added to, by the study of the effect of
chaning the phosphine ligand, a persistent feature in these Grubbs systems owing to its vital
importance in the catalytic activity [6] (just as the carbene function is), on the ability of the overall
complex to form ring product.

Experimental
All vacuums (during solvent removal and general Schlenk procedures) quoted below were at
pressures of ~7 101 (1 101 ) mbar, a PO2 of 1.5 101 mbar.
Synthesis of [RuCl2(PPh3)2(phenylindenylidene)] (catalyst 1)
RuCl2(PPh3)3 (0.2000 g, 0.2086 mmol) and 1,1-diphenyl-2-propyn-1-ol (1.5 molar equivalents) were
dissolved in THF (20 mL) and the resulting solution was refluxed for 3 hours. Upon cooling, the
solvent was removed in vacuo leaving a solid residue. The residue was redissolved in CH2Cl2 (ca. 2
2

Advanced Inorganic Research Practical Report William Hodds

mL), before the addition of hexane (20 mL), which precipitated a amorphous dark orange solid. The
reaction mixture was stirred vigorously (RT, 15 mins) until a homogenous solid precipitate was
obtained. The solids were isolated by filtration and washed with hexane (2 20 mL), before being
dried in vacuo, yielding catalyst 1 (~0.1295 g, 0.1461 mmol, 70%), a dark orange amorphous solid.
(This yield is approximate, and accounts for the solid removed for NMR and GC-MS analysis.
31

P-NMR: 29.03 ppm (Ru-PPh3)(relative to H3PO4). 1H-NMR: Phenyl hydrogen signals: 7.7 6.6 ppm,
1.47 ppm, s (alkyne), 1.19 ppm, d (hexane), 0.81 ppm, t (hexane).
Synthesis of [RuCl2(PCy3)2(phenylindenylidene)] (catalyst 2)
1 (0.0140 g, 0.0158 mmol) and PCy3 (0.150 g) were dissolved in CH2Cl2 (20 mL) and the resulting
solution was refluxed for 1.5 hours. Upon cooling, the solvent was removed in vacuo. The resulting
residue was suspended in hexane (20 mL) and stirred vigorously (RT, 30 mins) until a homogenous
solid precipitate was obtained. The solids were isolated by filtration and washed with hexane (2 20
mL), before being dried in vacuo, yielding 2 (0.0102 g, 0.0111 mmol, 70%).
31

P-NMR: 29.02 ppm (Ru-PCy3), 50.15 ppm (Cy3PO). 1H-NMR: Phenyl hydrogen signals: 7.8 6.6 ppm,
1.47 ppm, s (alkyne), 1.19 ppm, d (hexane), 0.81 ppm, t (hexane), 1.85 ppm (Cy signal), 1.38 (Cy
signal).
Grubbs-catalysed ring-closing metathesis of diethyl diallylmalonate
1 (0.0177 g, 0.02 mmol, 2.5 mol %) was dissolved in CH2Cl2 (5 mL) and diethyl diallylmalonate (0.2
mL, 0.2 g, 0.8 mmol) was added directly to the solution. The reaction mixture was stirred (RT, 1
hour). The solvent was removed in vacuo and pentane (ca. 5 mL) was added to the residue,
precipitating a solid. The mixture was filtered through magnesium sulfate and the resulting solution
was reduced to dryness, giving a red, crude oil (0.0775 g, 0.365 mmol, 45.64% crude yield) .
13

C-NMR: 170.69 ppm (e), 132.34 ppm (b), 119.04 ppm (a), 77.04 (CDCl3), 61.16 ppm (f), 57.24 ppm
(d), 36.74 ppm (c), 14.07 ppm (g). 1H-NMR: 5.66-5.52 ppm, m, 1H, b, 5.06-5.04 ppm, d, 1H, a, 5.01
ppm, s, 1H, a, 4.15-4.07 ppm, q, 2H, d, 2.58 -2.56 ppm, d, 2H, d, 1.2-1.15 ppm, t, 3H, e, 0.83 ppm, m,
H-Grease.
2 (0.0098 g, 0.0106 mmol, ~1.0 mol %) was dissolved in CH2Cl2 (5 mL) and diethyl diallylmalonate (0.2
mL, 0.2 g, 0.8 mmol) was added directly to the solution. The reaction mixture was stirred (RT, 1
hour). The solvent was removed in vacuo and pentane (ca. 5 mL) was added to the residue,
precipitating a solid. The mixture was filtered through magnesium sulfate and the resulting solution
was reduced to dryness, giving an oil (0.1585 g, 0.7471 mmol, 93.03% crude yield).
13

C-NMR: 170.69 ppm (e), 132.34 ppm (b), 119.04 ppm (a), 77.04 (CDCl3), 61.16 ppm (f + E), 57.24
ppm (d), 36.74 ppm (c), 14.07 ppm (g +F), 127.78 ppm (A), 172.19 ppm (D), 40.38 ppm (B). 1H-NMR:
5.66-5.52 ppm, m, 1H, b, 5.06-5.04 ppm, d +C, 1H, a, 5.01 ppm, s, 1H, a, 4.15-4.07 ppm, q, 2H, d,
2.58 -2.56 ppm, d, 2H, d, 1.2-1.15 ppm, t, 3H, e +D, 0.83 ppm, m, H-Grease, 5.33 ppm, s, A, 2.94
ppm, s, B.

Advanced Inorganic Research Practical Report William Hodds

Results

13

C-NMR, 1H-NMR and GC-MS of crude RCM product oil

a
a

TMS

Fig x. 1H-NMR of RCM reaction product oil (obtained using catalyst 1), showing purely DEDAM and no ring product.

H Grease

Advanced Inorganic Research Practical Report William Hodds

Chloroform-d

Fig x. 13C-NMR of RCM reaction product oil (obtained using catalyst 1), showing purely DEDAM and no ring product.

TMS

Advanced Inorganic Research Practical Report William Hodds

a'

a
c
a'

d+C

B
A

e+D

TMS

Fig x. 1H-NMR of RCM reaction product oil (obtained using catalyst 2), showing purely DEDAM and some ring product.

H Grease

Advanced Inorganic Research Practical Report William Hodds

f
e

Chloroform-d

f+E

g+F

Fig x. 13C-NMR of RCM reaction product oil (obtained using catalyst 2), showing purely DEDAM and ring product.

e
C

Advanced Inorganic Research Practical Report William Hodds

It can be deduced from the above 13C and 1H NMR spectra that no RCM product was made to any
1 significant
(0.0177 g, extent
0.02 mmol,
mol %)
dissolved
CHinferred
andthe
diethyl
diallylmalonate
(0.2
2Cl2 (5 mL)
when2.5
catalyst
1 was used.
Thisinwas
from
absence
of any signals
in
1
13
mL,
g, 0.8 appropriate
mmol) was added
to theinsolution.
reaction
mixtureand
wasonly
stirred
(RT, 1
any0.2
regions
to the directly
ring product
both theThe
H and
C spectra,
signals
hour).
solvent
was removed
in DEDAM,
vacuo and
pentane
(ca. 5All
mL)
was added in
tothe
theabove
residue,
arisenThe
from
the starting
material,
were
observed.
assignments
NMR
spectra
are
supported
by
computationally-predicted
assignments
of
DEDAM
and
the
RCM
ring
precipitating a solid. The mixture was filtered through magnesium sulfate and the resulting solution
product
[7].to dryness, giving a red, crude oil.
was
reduced
It was observed,
however, that catalyst 2 was successful in allowing for the production of a non13C-NMR
+ 1H-NMR
zero quantity of RCM product, as the appearance of new signals in both the 13C NMR and 1H
2 NMR
(0.0185
spectra
g, 0.02
aremmol,
indicative
2.5 mol
of a%)
new,
wasbut
dissolved
similar in
species,
CH2Cl2fitting
(5 mL)the
andprofile
diethyland
diallylmalonate
an RCM product
(0.2
mL,
of DEDAM.
0.2 g, 0.8 mmol) was added directly to the solution. The reaction mixture was stirred (RT, 1
hour). The solvent was removed in vacuo and pentane (ca. 5 mL) was added to the residue,
precipitating
It is also later
a solid.
seen that
The mixture
GC-MS analyses,
was filtered
of TIC
through
chromatographs
magnesiumand
sulfate
fragmentation
and the resulting
patterns,
solution
was
support
reduced
thisto
finding,
dryness,
andgiving
the rationalisation
an oil. [ ]
of catalyst 1 activity vs catalyst 2 activity is also
discussed in greater detail in the discussion section.
13C-NMR + 1H-NMR

DCM, RT, 45 min

DCM, RT, 45 min

Fig x. [RuCl2(PPh3)2(phenylindenylidene)] (catalyst 1) is unable to catalyse the RCM of DEDAM at RT,

whereas [RuCl2(PCy3)2(phenylindenylidene)] (catalyst 2) is able to catalyse the RCM of DEDAM at RT.

Advanced Inorganic Research Practical Report William Hodds

All GC-MS spectra, of the RCM crude product oils, were collected using TOF EI+ method recording
over 10 minutes, with TIC (total ion current) chromatograms. The column used was a Phenomenex
ZB-1MS low polarity column, length = 30 m, 250 m internal diameter, 0.25 m film thickness.

IMPURITY OR

Figure x. GC TIC chromatograph of the crude RCM product oil, using catalyst 1.
The low intensity peak at 5.71 min is attributed to the RCM product due the corresponding
fragmentation pattern (see later), and the higher intensity peak at 5.99 min is attributed to the
starting material diethyl diallylmalonate (DEDAM). This assignment is also supported by the elution
order on this low polarity column. An impurity at 5.71 was also suspected, so this peak at 5.71 min
may well be the basal level of impurity, of which RCM product would add to
As an impurity is suspected to co-elute with the RCM product, it was judged that no fragmentation
pattern for the peak at 5.71 be provided here, however later, when product is suspected to have
formed, a combined fragmentation pattern of impurity and RCM product is analysed.

Advanced Inorganic Research Practical Report William Hodds

Figure x. TOF EI+ MS expansion of the 5.99 min signal, for the crude RCM product oil, using catalyst
1. The proposed species attributed to the major highlighted signals are shown below.

m/z = 199
a=

b=

m/z = 153

m/z = 125
c=

d=

e=

10

m/z = 93

m/z = 41

Advanced Inorganic Research Practical Report William Hodds

The fragment ion of m/z = 41 is of particular significance, as it is diagnostic of the linear alkene
function, as seen in DEDAM. This indicates that this fragmentation pattern, arising from GC peak at
5.99 min, cannot belong to a cyclic alkene, and thus cannot belong to the RCM product, supporting
the assignment of this peak to DEDAM. The absence of a signal at m/z = 41 in the TOF MS expansion
spectrum of the GC peak at 5.71 further reinforces this assignment.

IMPURITY AND/OR

Fig x. GC TIC chromatograph of the crude RCM product oil, using catalyst 2. Note the increased peak
area of the peak at 5.71 min as opposed to the same peak in fig. x, indicating a greater quantity of
the RCM product present.
Immediately, it can be seen that the peak area of the 5.71 min RCM product signal is greater in this
GC TIC chromatograph than in fig. x, indicative of a non-zero quantity of the RCM product, using
catalyst 2 than with catalyst 1. No peak area values were obtainable for the RCM product signals for
either chromatographs, so this increase in % conversion of DEDAM cannot be quantified
unfortunately.

11

Advanced Inorganic Research Practical Report William Hodds

d
c

b
a

Fig x. The TOF MS expansion of the GC peak at 5.71 min, the RCM product peak, using catalyst 2.
Fragment ions of significance have been highlighted and their identities are proposed below.
a, M+ =
m/z = 212

b=

m/z = 166

c=

m/z = 138

d=

m/z = 66

12

Advanced Inorganic Research Practical Report William Hodds

The prominent signal at m/z = 79 could not be identified, however a complex rearrangement
product is suspected, as no simple fragmentation gives rise to an ion with a m/z of 79.0. Regardless,
the fragmentation pattern shows support of the GC peak at 5.71 min originating from the RCM
product.

Fig x. TOF EI+ MS expansion of the 5.99 min signal, for the crude RCM product oil, using catalyst 2.
The proposed species attributed to the major highlighted signals are shared with those in fig. x.
It can be seen that, from the GC-MS spectra presented, product was potentially not made for both
complexes, more product was made using the catalyst 2 (PCy3), as can be inferred qualitatively from
the peak areas of the 5.71 min peaks of each respective GC TIC chromatograph.

13

Advanced Inorganic Research Practical Report William Hodds

31

P-NMR, 1H-NMR of catalysts 1 and 2

All NMR spectra taken using a 300 MHz NMR spectrometer, consisting of a Bruker AVIII300NB
UltraShield magnet, an Avance III console and 60 position SampleXpress autosampler.

Ru - PPh3

Fig x. The low resolution 31P-NMR spectrum of catalyst 1, showing one prominent, high intensity
signal at 29.03 ppm.
The presence of a single signal is readily rationalised by the noting of the C2 axis of symmetry along
the carbene-Ru bond, making both PPh3 groups equivalent by symmetry.
The chemical shift of this signal is also in agreement with similar spectra taken by Frstner et al [8],
who report a peak an equivalent peak at 28.70 ppm, relative to the standard H3PO4.

C2

Fig x. Generalised catalyst 1 (R = Ph) and catalyst 2 (R = Cy) structure showing the C2 axis of
symmetry along the carbene-Ru bond, rendering both PR3 ligands equivalent by symmetry.
Considering that the Chauvin mechanism for carbene-catalysed RCM requires the initial dissociation
of a ligand to form the reactive 14 e complex [9], it is worth seeking a signal for free PPh3, reported
to be at -6 ppm (relative to H3PO4) [f]. No such signal is observable above the baseline (~40%), so it
can be inferred that the PPh3 ligand is not labile in this complex, and does not exist free in solution,
in equilibrium, with the Grubbs complex, to any significant extent. This finding is also reported by
Dias et al [10].

14

Advanced Inorganic Research Practical Report William Hodds

However the peak at 29 ppm could just as readily be assigned to the trans phosphine ligands of the
starting material, RuCl2(PPh3)3, which have the same symmetry relationship, and likely a similar
chemical shift value to catalyst 1.
A 31P-NMR of the RuCl2(PPh3)3 complex prior to mixing and reaction with other components would
provide the value for the phosphine ligands in this complex, and therefore would have allowed for
an assignment of the observed 31P signal to starting material or product, however this was not done,
and the values for this complex, although highly used in similar studies, is not found readily in the
literature.
Phenyl hydrogens
SM*
*

Hexane

Predicted a region

Fig x. 1H-NMR of catalyst 1 (TMS signal at 0 ppm omitted), showing expansion region 0.75 ppm
1.25 ppm where ill-resolved doublet, 1.19 ppm (JHH unclear) and triplet, 0.81 ppm (JHH unclear)
feature.
The poor resolution of peak splitting disallowed a legitimate comparison of JHH coupling constants,
attempts gave a JHH of 3 Hz for peak at 1.19 ppm, but for peak at 0.81 ppm gave 6 Hz if the downfield
peak was used, and 9 Hz if the upfield peak was used, despite the overall peaks belonging to a triplet
(and therefore should have equivalent coupling constants). The qualitative multiplicity was therefore
used, along with chemical shifts, to assign these peaks to the hexane used in the procedure for
washing the crude product. This assignment is also supported by similar assignments in the
literature, in chloroform-d [11].

15

Advanced Inorganic Research Practical Report William Hodds

*The peak at 1.47 ppm has been attributed to the starting material alkyne, 1,1-diphenyl-2-propyn-1ol, terminal hydrogen of the alkyne bond. Considering that there is no NMR evidence at this point of
catalyst 1 formation, the presence of SM is to be expected.
In addition, no discernible peak for hydrogen a is observed within the expected region of
4.7 (0.1) ppm, indicating further that catalyst 1 did not form to any significant degree.

By-product
OR
Ru-PCy3

Ru (PCy3)2

Fig x. 31P-NMR of catalyst 2, showing the ruthenium-bound (PCy3)2 signal at 29.03 ppm, and a
distinct peak at 50.15 ppm, the proposed Ru - PCy3 signal.
It would be expected that the signal for the ruthenium-bound to a phosphine ligand more donating than PPh3 would exist at a higher ppm, according to the increased electron density donated
to the Ru centre [12] (and less on the P atom), such a peak is reported at 32 ppm [13]. Here,
however, no such increase in ppm (relative to PPh3) is observed, suggesting no significant catalyst 2
formation. The idea that catalyst 2 did not form is in direct contradiction with previous results, the
13C and 1H analysis of the RCM product oils, so it is possible that there is a small signal at 32 ppm,
which cannot be observed due to the large deviation of the baseline, or that the shift in ppm relative
to PPh3 is negligible.
In addition, an anomalous, high intensity peak at 50.15 ppm is observed, a chemical shift entirely
unlike that of free PCy3, 10.50 ppm [14]. As such, the species giving rise to this signal must be a
reaction side product or degradation product, potentially a phosphorus (V) species, due to P(III)
P(V) oxygen oxidation product, as the typical 31P chemical shift for a trialkyl P(V) species is around 50
ppm. Et3PO giving rise to a peak at 48.3 ppm [15], it is therefore not unrealistic to propose the 50.15
ppm peak is Cy3PO. If so, there has been significant Grubbs catalyst air-oxidation during the
spectrum-taking process.
It has been proposed that this 50 ppm signal is actually the monophosphine Ru complex (in a similar
but not identical Ru complex) [16], a known intermediate of the Chauvin mechanism, and that the 29
ppm signal is the bisphosphine Ru complex. This is the preferred interpretation as it fits the results
collected here better, given RCM product formed when catalyst 2 was employed.
16

Advanced Inorganic Research Practical Report William Hodds

Phenyl hydrogens

SM
Hexane

Predicted a region

H2O
Cy*

Cy*

a, d

b, t

Fig x. 1H-NMR spectrum of catalyst 2, showing expansion of the region 0.7 ppm 3 ppm where the
potential assignments for a (1.19 ppm) and b (0.82 ppm) exist, along with many poorly-resolved
peaks suspected to be cyclohexyl hydrogens.
It can be seen in the above spectrum that the a and b environments are potentially still recorded,
judged by the expected multiplicity and chemical shifts inferred from the 1H spectrum of catalyst 1.
However, new and very poorly resolved peaks have appeared within a similar region. This region is
diagnostic of alkyl environments, so these broad peaks may well be the cyclohexyl environments,
broadened due to the dissociation of the PCy3 ligand into solution at a rate nearly comparable to the
NMR timescale (~10-1 ms [17]).
The chemical shift ranges for Cy hydrogens in catalyst 2 are reported to be within the region 2.6 ppm
1.18 ppm [18], discovered via high resolution 2D NMR experiments, supporting the proposed
assignment of Cy hydrogens to the broad peaks in fig. x.
17

Advanced Inorganic Research Practical Report William Hodds

Again, no peak attributable to hydrogen a is observed within the predicted region, however this is
not surprising, as the synthesis of catalyst 2 depended critically on the synthesis of catalyst 1
(catalyst 1 being a SM), and previous 1H-NMR and 31P-NMR spectra suggest no significant formation
of catalyst 1, so it is highly probable no catalyst 2 has formed significantly either.
It is possible, however, that the a signal is masked by the aromatic region, as further results point
toward RCM product formation with catalyst 2, which strongly suggests that catalyst 2 did form at
some stage, which also infers that catalyst 1 did form at some stage.

Discussion
Olefin metathesis, when catalysed by a Grubbs catalyst, proceeds predominantly via the dissociative
pathway (as opposed to the associative pathway [19]), which is shown below:

X=

Fig x. The dissociative olefin ring closing metathesis (RCM) mechanism, showing the involvement of
the ruthenium Grubbs catalyst.
In this mechanism, the PR3 ligands can influence the rate of catalytic turnover by two roles:
- Via the rate of PR3 ligand dissociation.
18

Advanced Inorganic Research Practical Report William Hodds

- Via the exertion of trans-effect on any ligand trans to itself (ie, making the trans ligand more labile).
This could be relevant to the other PR3 ligand in the initial dissociation step, or the coordinated
pendant alkene in the relevant steps.

The consensus amongst Grubbs and researchers in this field is that the dissociation of the PR3 ligand
is the key step of which the nature of phosphine ligand influences the rate of RCM [o], concluded by
the observed trend in which larger, more sterically-bulky phosphine ligands, as well as those which
have significant -donor ability, give higher rates of RCM [20] [21] [22].
This trend is readily rationalised by the fact that larger ligands will incur destabilising steric clashes
with other ligands in close proximity, and as such the kinetic barrier to dissociation will be lower by
virtue of the ground state energy being higher than with a smaller ligand. -donor ability is also
important as a strong -donor ligand will enrich the Ru centre more so than a poor -donor ligand, it
then follows that the metal-ligand molecular orbitals (MOs) of the trans ligand will be enriched,
including any antibonding MOs, thereby destabilising the metal-ligand interaction and promoting
ligand dissociation of this trans ligand. This is the foundation of the trans effect, and may well have
relevance in considering the effect of phosphine ligand influence in the rate of Grubbs catalysed
RCM. It can also be speculated that the -donor activity of the ligand will also stabilise the vacant cis
coordination site in the 14 e- intermediate, much to the same outcome [23].
Comparison of PPh3 catalyst (catalyst 1) with PCy3 catalyst (catalyst 2)
From the 1H-NMR, 13C-NMR and GC-MS data presented in the experimental section, it can be
deduced that catalyst 1 showed little/no catalytic activity, giving no product peak discernible above
the impurity peak in the GC TIC chromatograph, no ring product 13C environment signals and no ring
product 1H signals.
In contrast, catalyst 2 yielded a non-zero ring product turnover, as can be inferred from the same
type of spectra, but with actual presence of product environments (though the proton environment
adjacent to the carbene bond was still absent), when collected for mixtures that employed catalyst
2.
This observation is much of the same trend observed by Grubbs et al, Jimenez et al, and Sanford and
Ulman et al, as PPh3 (Vmol = 232.7 cm3 mol-1) * is both smaller than PCy3 (Vmol = 288.1 cm3 mol-1) *
and a poorer -donor ligand than PCy3 ( (PPh3) = 13.45, (PCy3) = 1.4) [24], it is expected that the
catalytic turnover at a fixed time compared across both ligand complexes will be lower for PPh3 than
for PCy3, which is what has been shown here.
*Vmol computationally calculated using HSPiP software DIY functionality, and serves as a value of
steric size, much like the cone angle of the Tolman parameters. For this simple system, Vmol is
sufficiently explanatory, however more complex systems require the more rigorous treatment
afforded by cone angle values.

19

Advanced Inorganic Research Practical Report William Hodds

Conclusion
Catalyst 1 does not significantly catalyse the ring-closing metathesis of diethyl diallylmalonate, as
can be inferred from the absence of signals corresponding to 13C and 1H environments in NMR
measurements taken from supposed product oils, as well as the lack of a characteristic
fragmentation pattern from the product peak in the MS TOF spectrum taken from the same oil.
Conversely, catalyst 2 does give a non-zero catalytic turnover in the 45 min reflux conducted, as
indicated by the inverse of the previously mentioned data. This has been interpreted as the effect of
the phosphine ligand in each of the complexes, respectively. The larger, more strongly -donating
PCy3 ligand more readily dissociates to form an active, 14 e- Ru intermediate, the key active species
as postulated by the Chauvin mechanism, which then goes on to bind to the pendant alkene of the
substrate (here, DEDAM). This has been explained by the steric clashing of the PCy3 ligand exerting a
destabilising effect on the coordination of this ligand to the Ru centre, and the trans-influence the
PCy3 ligand has both in the mono (stabilises the vacant coordination site via enriching the deficient
14 e- Ru centre) and bis-phosphine (labilises the trans PCy3 ligand, promoting dissociation
thermodynamically) intermediates in the mechanism.
As such, for maximal catalytic activity (that a change in dissociative ligand may bring), large
phosphines are recommended during the synthesis and design of new 1st generation Grubbs
catalysts.

References
[17] Farrar, T. C.. and Becker,E. D.."Pulse and Fourier Transform NMR,"AesdemicPress, New York,
1971.
[13], [14], [8], [18] Frstner, A., Guth, O., Dffels, A., Seidel, G., Liebl, M., Gabor, B. and Mynott, R.
(2001), Indenylidene Complexes of Ruthenium: Optimized Synthesis, Structure Elucidation, and
Performance as Catalysts for Olefin MetathesisApplication to the Synthesis of the ADE-Ring
System of Nakadomarin A. Chem. Eur. J., 7: 48114820.
[10], [14] http://wanbin.sjtu.edu.cn/html/free%20resourse/31P%20NMR%20Chemical%20Shift%20of%20P(III)
%20Compounds.pdf, accessed 14/10/2016.
[15] http://mutuslab.cs.uwindsor.ca/schurko/nmrcourse/chemical_shifts/31P_chemical_shifts.htm,
accessed 14/10/2016.
[12] - Fulmer, Gregory R., et al. "NMR chemical shifts of trace impurities: common laboratory
solvents, organics, and gases in deuterated solvents relevant to the organometallic
chemist." Organometallics 29.9 (2010): 2176-2179.
[7] - http://www.nmrdb.org/new_predictor/index.shtml?v=v2.66.0, accessed 15/10/2016.
[16] - Sanford, M.S.; Ulman, M.; Grubbs, R.H. New insights into the mechanism of ruthenium
catalyzed olefin metathesis reactions. J. Am. Chem. Soc. 2001, 123, 749750.
[16], [18], [13] Jimenez, Leonel R., et al. "Development of a Method for the Preparation of
Ruthenium Indenylidene-Ether Olefin Metathesis Catalysts." Molecules 17.5 (2012): 5675-5689.

20

Advanced Inorganic Research Practical Report William Hodds

[20], [19], [17], [19], [9], [11] - Eric L. Dias , SonBinh T. Nguyen , and Robert H. Grubbs * J. Am. Chem.
Soc., 1997, 119 (17), pp 38873897
[1] - Y. S. Tsantrizos, J.-M. Ferland, A. McClory, M. Poirier, V. Farina, N. K. Yee, X.-J. Wang, N. Haddad, X. Wei, L. Zhang, J. Organomet. Chem. 2006, 691, 51635171.
[2] - Naoya Kanbayashi, Taka-aki Okamura, and Kiyotaka Onitsuka. Macromolecules 2015 48 (23),

8437-8444.
[3] - Ellen C. Gleeson, W. Roy Jackson, Andrea J. Robinson, Ring-closing metathesis in peptides,
Tetrahedron Letters, Volume 57, Issue 39, 28 September 2016, Pages 4325-4333, ISSN 0040-4039.
[4] - Y. Chauvin, Angew. Chem. 2006, 118, 38243831; Angew. Chem. Int. Ed. 2006, 45, 37403747
(Nobel Lecture).
[5] - Hendrik J. van der Westhuizen, Andreas Roodt, Reinout Meijboom, Kinetics of thermal
decomposition and of the reaction with oxygen, ethene and 1-octene of first generation Grubbs
catalyst precursor, Polyhedron, Volume 29, Issue 14, 22 September 2010, Pages 2776-2779, ISSN
0277-5387
[6], [21] - Michle E Cucullu Chunbang Li Steven P Nolan SonBinh T Nguyen Robert H Grubbs
Organometallics 1998, Vol.17(25), p.5565-5568

21

Advanced Inorganic Research Practical Report William Hodds

22