I5.

EXPERIMENT I5

THE PREPARATION OF TRIPHENYLPHOSPHINE AND SOME OF ITS

COMPLEXES WITH TRANSITION METALS

A variety of trivalent phosphorus compounds give complexes with transition metals,

and these complexes are widely used as starting materials for the preparation of
transition metal organometallic complexes. The two common routes for the
preparation of trivalent phosphorus compounds:

3 PhMgBr + PCl3  PPh3 + 3 MgBrCl

3 PhLi + PCl3  PPh3 + 3 LiCl

are typical of the routes used to prepare many metal-aryl complexes. The
phosphines (or phosphanes to use the more modern name), PR 3, and phosphites,
P(OR)3, are donor molecules (via the lone pair on the phosphorus atom) and can act
as Lewis bases:

PR3 + BR3  R3P-BR3

The phosphines also have empty d orbitals and back-acceptance into these orbitals
is also possible.

The extent to which back-donation occurs is dependant on the electronegativity of

the groups attached to the phosphorus atom. For the Group 15 ligands this effect is
reflected in the CO stretching frequencies.

Compound  CO (cm1)
[(C2H5)3P]3Mo(CO)3 1937 1941
[(C2H5O)3P]3Mo(CO)3 1994 1922
[Cl2(C2H5O)P]3Mo(CO)3 2027 1969
(Cl3P)3Mo(CO)3 2040 1991
(F3P)3Mo(CO)3 2090 2055
 I5.2

Based on these and other data an extensive series of ligands including phosphorus
donor ligands as well as other Group 15 and Group 16 ligands can be arranged in
terms of -acidity (the  acidity series).

A consideration of the actual stability of the metal-phosphine complexes shows that

steric as well as electronic factors are important. This is revealed in the equilibrium
data below:

Equilibrium Constants in Benzene at 25C

These steric angles can be correlated with a parameter introduced by C.A. Tolman
called the cone angle. This cone angle is defined as the apex angle of a cylindrical
cone centred 2.28  from the centre of the P atom which just touches the Van Der
Waals radii of the outermost atoms of the model. The smaller the cone angle the
greater the competitive binding ability of the ligand in situations where steric
interference is important. Cone angle data for a number of phosphorus ligands are
given below.

Values of the ligand cone angle, 

PMe3 118
PMe2Ph 122
PPh2Me 136
PPh3 145
PCy3 170
 I5.3

EXPERIMENTAL

Triphenylphosphine is prepared from a Grignard reagent (PhMgBr) and PCl 3. The

product is then used to prepare complexes of Co(II), Ni(II) and Cu(I). U.V. spectra
are to be recorded.

PREPARATION OF PHENYL MAGNESIUM BROMIDE

All apparatus must be dried in an oven before use, and assembled as in Figure 1.
Magnesium turnings (0.3 g) are placed in a 3 necked 50 mL round bottom flask fitted
with a reflux condenser and a dropping funnel. Bromobenzene (0.4 mL), dry diethyl
ether (1 mL) and a stirring bar are added to the flask. (Note: Dry ether must be
used.) On warming gently with the hand the reaction should begin as evidenced by
bubble formation. If the reaction does not start (a) see a demonstrator, or (b) add a
crystal of iodine.

Once the reaction has commenced add, over a 5 minute period, a solution of
bromobenzene (1 mL) and dry diethyl ether (5 mL) from the dropping funnel at such
a rate that the other refluxes gently. Reflux for a further 15 minutes over a warm
water bath to ensure complete reaction. The solution should now be cloudy and
brown.

PREPARATION OF TRIPHENYULPHOSPHINE
The reaction should be carried out in a fume cupboard.
The Grignard reagent should be stirred whilst cooling in an ice bath. A solution of
phosphorus trichloride (0.21 mL) in dry diethyl ether (5 mL) is added dropwise to the
Grignard reagent from a dropping funnel over a period of 5 minutes. A vigorous
reaction occurs, as each drop enters a yellow solid may begin to separate; if it does
then the addition is being made too rapidly.

Prepare a solution of hydrochloric acid (3 mL of concentrated acid in 20 mL of water)

and place this in a 400 mL beaker surrounded by an ice-salt freezing mixture.
Slowly pour the contents of this reaction flask into the acid, a little at a time, with
vigorous stirring. When the hydrolysis is complete the bulk of the triphenylphosphine
will be in the ether layer. Decant off the ether layer, extract the aqueous layer with a
further 2.5 mL of ether and dry the combined ether fractions over anhydrous sodium
sulphate until the ether is clear. Filter off and evaporate the filtrate to obtain a yellow
semi-liquid liquid residue which solidifies overnight to yield 0.7 g of crude
 I5.4

triphenylphosphine. Recrystallize the product from ethanol, retaining a few particles

of the solid to seed the cooled ethanolic solution. Filter off the white crystalline
triphenylphosphine in a Buchner funnel, washing the product with 1 mL portions of
ethanol until all traces of yellow colour have disappeared. Melting-point 79-80C.

PREPARATION OF TRIPHENYLPHOSPHINE COMPLEXES

(a) [Co(PPh3)2Cl2]. Dissolve finely powdered pink cobalt(II) chloride

(CoCl2.6H2O) (0.11 g; 0.4 mmole) in absolute ethanol (1.5 mL) to obtain a rich blue
solution. Add a solution of triphenylphosphine 0.25 g; 0.8 mmole) in absolute alcohol
(2 mL) (heat if necessary) to obtain an immediate precipitate of bright blue crystals
which are collected in a Buchner funnel and washed with a little absolute ethanol
before drying. Report the yield and the melting point. Record the UV-vis spectrum
of the compound in a suitable solvent, give the concentration on the printout (hint:
what solvent was the compound precipitated from? Is the compound charged?)

(b) [Ni(PPh3)2Cl2]. Stir nickel(II)chloride (NiCl6.6H2O) (0.20 g; 0.8 mmole) in

acetic acid (8 mL) to obtain a very dark-green crystalline precipitate which becomes
almost black on standing. Filter off in a Buchner funnel and wash with ether to
remove unreacted triphenylphosphine, and then a little acetic acid before drying.
Report the yield and the melting point.

(c) [Cu(PPh3)Cl]4. Dissolve copper(II) chloride (CuCl2.2H2O) (0.10 g: 0.6

mmole) in ethanol (3 mL) to obtain a green solution. Add a solution of
triphenylphosphine (0.25 g); 0.8 mmole) in ethanol (5 mL) and heat the mixture
under reflux for a short time until the green colour disappears indicating that the
copper(II) has been reduced to copper(I) by the triphenylphosphine. At the same
time an off-white solid is deposited, which is filtered off in a Buchner funnel and
washed with ethanol (2 cm3) to obtain fine pale-beige crystals. Report the yield and
the melting point.

Thus, triphenylphosphine is prepared from a Grignard reagent rather than

phenyllithium as the latter is air-sensitive and requires an inert atmosphere for good
yields. Reaction of triphenylphosphine with the metal salts yields stable complexes.
These are readily characterized by U.V. spectroscopy. They could be further
reacted with more Grignard reagent to yield metal-carbon bonded complexes e.g.:

(M=Co, Ni)
[M(PPh3)2Cl2] + 2PhMgBr [Ph2M(PPh3)2] + 2MgBrCl
 I5.5

Phosphines, (especially triphenylphosphine, because of its stability in air) have been

used as ligands in thousands of organometallic complexes. Some of these
complexes e.g. Wilkinson's catalyst, Rh(PPh3)3Cl are of great commercial
importance.

REPORT

1. Report any variations from the experimental procedure listed.

2. Report percentage yields and melting points as indicated.

3. Visible spectra and their assignments must also be reported for the Co(II)
complex only.

4. Look up the cone angle of PPh(1Bu)2. Comment on its size ( value).

5. Would  for PMe3 increase or decrease if the MP bond distance increased
from 2.28 . Show your reasoning.

6. Explain clearly and concisely the origin of the trends in the carbonyl stretching
frequencies of the complexes given on the first page of this practical.

7. Do the complexes Rh4(Co)11(PPh3), (5-C5H5)Re(CO)(PPh3)I, and

Co2(CO)6(PPh3)2 obey the 18 electron rule? Draw possible structures for the
complexes. You may wish to look up related structures in a text book if
necessary.

REFERENCES

1. C.A. Tolman, Chem. Reviews, 77, 313 (1977)

2. F.R. Hartley, "Elements of Organometallic Chemistry", Chemical Society,

London, 1974.