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Experiment 4: Preparation and characterisation of ruthenium complexes:

organometallic catalyst containing carbonyl, hydride, and phosphate ligands.

Introduction

The platinum group metals (i.e. Ru, Rh, Pd, Os, Ir, and Pt) have outstanding catalytic properties due
to their ability to form compounds with different oxidation states. Rhodium for example has a very
extensive chemistry involving oxidation states ranging from -2 to +8. A notable application of
rhodium is to catalyse the decomposition of noxious nitrogen oxides into benign nitrogen and
oxygen in car exhaust system (Equation 1).

𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡
2𝑁𝑂𝑥 𝑥𝑂2 + 𝑁2 (Eq. 1)

Ruthenium is another example, which has been shown to promote olefin metathesis with important
applications in organic and pharmaceutical chemistry (Figure 1).

Figure 1. The reaction consists of an alkene double-bond cleavage followed by a statistical redistribution of alkylidene
fragments.

Halides of the platinum group metals can be reduced by alcohols in the presence of ligands to give
carbonyl and/or hydrido complexes via a β-elimination step. In this experiment [Ru(CO)H2(PPH3)3]
and [Ru(CO)ClH(PPH3)3] will be synthesised via this method – where the source of the hydride is the
CH2 group of the primary alcohol and the source of the CO ligand is the aldehyde.

A third complex, [Ru(OAc)(CO)H(PPH3)2], is obtained by the migration of an R group from carbon to


the metal.
Aims

 Explore synthetic routes to complexes with carbonyl, hydride, and phosphine ligands
 Use characterisation techniques, especially multinuclear NMR and IR spectroscopy

Method

Preparation of carbonyldihydridotris(triphenylphosphine)ruthenium(II), [Ru(CO)H2(PPH3)3]

Triphenylphosphine (1.0 g, 0.038 mol) and ethanol (20 ml) were heated to reflux with stirring. To this
was the quick and successive addition of ruthenium trichloride hydrate (0.15 g, 0.576 mol) in ethanol
(10 ml), formaldehyde (40% aqueous, 10 ml), and potassium hydroxide (0.5 g, 89 mol) in ethanol (10
ml). The mixture was allowed reflux for a further 15 min and then removed from heat. The solid was
collected via vacuum filtration and washed with ethanol (5 ml), then water (5 ml), followed by
ethanol (5 ml) again. The product was dissolved in a minimal amount of dichloromethane and
filtered through a 2 cm neutral alumina column before the column was flushed with
dichloromethane (2 ml). Ethanol was added dropwise to induce precipitation and the mixture
allowed to stand for 1 hr. The pink crystals (0.11 g, 18%) were collected by vacuum filtration and
stored in a darkened desiccator.

Preparation of carbonylchlorohydridotris(triphenylphosphine)ruthenium(II), [Ru(CO)ClH(PPH3)3]

Triphenylphosphine (1.0 g, 0.038 mol) and 2-methoxyethanol (30 ml) were heated to reflux with
stirring. To this was the dropwise addition of ruthenium trichloride hydrate (0.15 g, 0.567 mmol)
with 2-methoxyethanol (10 ml) followed by formaldehyde (40% aqueous, 10 ml). The mixture was
allowed to reflux for a further 20 min and then ethanol (20 ml) added. The mixture was removed
from heat and cooled in ice. The creamy solid (0.09 g, 15%) was collected by vacuum filtration,
washed successively with water (10 ml) and ethanol (10 ml), then stored in a darkened desiccator.

Preparation of (acetato)carbonylhydridobis(triphenylphosphine)ruthenium(II),
[Ru(OAc)(CO)H(PPH3)2]

Carbonylchlorohydridotris(triphenylphosphine)ruthenium(II) (0.32 g, 0.325 mmol) and 2-


methoxyethanol (5 ml) were heated to reflux with stirring under nitrogen. Acetic acid (0.5 ml) was
added before the mixture was allowed to reflux for a further 10 min under nitrogen and then
removed from heat. The dark yellow crystals (0.20 g, 79%) were collected by vacuum filtration,
washed successively with ethanol (10 ml), water (10 ml), and ethanol (10 ml), and then stored in a
darkened desiccator.
Question 1

The six platinum group metals are; platinum, osmium, iridium, ruthenium, rhodium, and palladium.

Question 2

[Ru(CO)H2(PPH3)3]

A peak due to carbonyl stretch is clearly visible at 1937.96 cm-1. This is slightly lower than the
stretching frequency of free CO (2157 cm-1) due to the presence of triphenylphosphine. Strong σ-
donors such as PPh3 lead to an electron rich centre, so that the π-antibonding orbital is more highly
populated and the CO bond is weakened. Consequently the stretching frequency decreases.
Terminal metal-hydrogen bonds are observed at 2358.76 and 2341.09 cm-1.

[Ru(CO)ClH(PPH3)3]

A carbonyl peak is clearly visible at 1924.35 cm-1. A terminal metal-hydrogen peak is observed at
2101.60 cm-1.

[Ru(OAc)(CO)H(PPH3)2]

A carbonyl peak is clearly visible at 1972.20 cm-1. A terminal metal-hydrogen peak is not observed in
this spectra. The C=O stretch of the acetate ligand is observed at 1620.01 cm-1.

Question3

[Ru(CO)H2(PPH3)3]
[Ru(CO)ClH(PPH3)3]

[Ru(OAc)(CO)H(PPH3)2]
Question 4

Table 1. 1H NMR spectra

Compound Peak /ppm Splitting Coupling constants /Hz


6.5 to 8.0 Multiplet -
[Ru(CO)H2(PPH3)3] -6.9 Triplets of doublets of doublets 30.30, 16.17, 7.08
-8.9 Doublets of triplets of doublets 73.71, 28.29, 5.28
6.9 to 8.0 Multiplet -
[Ru(CO)ClH(PPH3)3]
-7.2 Doublet of triplets 144, 28
6.9 to 7.5 Multiplet -
1.5 Singlet -
[Ru(OAc)(CO)H(PPH3)2]
0.5 Singlet -
-16.1 Triplet 21.9

Table 2. 31P-1H NMR spectra

Compound Peak /ppm Splitting Coupling constants /Hz


[Ru(CO)H2(PPH3)3] 47 Triplet of doublets 23.12, 5.55
59 Doublet 17.57
[Ru(CO)ClH(PPH3)3] 15 Singlet -
41 Singlet -
[Ru(OAc)(CO)H(PPH3)2] 40 Singlet -

Question 5

[Ru(CO)H2(PPH3)3]

The 1H NMR spectra of this compound displays a triplet of doublets of doublets at -6.9 ppm
corresponding to cis-PPH3, cis-PPH3, and cis-hydrogen respectively. A doublet of triplets of doublets
at -8.9 ppm corresponds to trans-PPH3, cis-PPH3, and cis-hydrogen respectively. Hence the
compound must be;
[Ru(CO)ClH(PPH3)3]

The 1H NMR spectra of this compound displays a doublets of triplets at -7.2 ppm corresponding to
trans-PPH3 and cis-PPH3 respectively. From the IR spectra, the unusually low carbonyl stretching
frequency indicates PPH3 trans to CO. Hence the compound must be;

Question 6

We can compare the spectra against deuterated compounds.

Question 7

The 1H NMR spectra displays a triplet at 16.1 ppm (21.9 Hz) corresponding to trans-PPH3. IR
spectroscopy can be used to establish the bidentate coordination of the acetate ligand. For
bidentate groups with equalised bonds the frequency of the anti-symmetrical vibration is lowered.
Hence the small C=O stretch of the acetate ligand (at 1620.01 cm-1) compared to the carbonyl group
(at 1972.2 cm-1) is indicative of a bidentate coordination.

Question 8

Because of molecular motion at room temperature, some chemical shifts average out during the
course of the NMR experiment to form a broadened peak.