Chemistry 141 Fall 2004

Various Oxidation State Complexes of Gold

Introduction
Gold is at the end of the transition metal series and has one of the highest

electronegativities of the metals. This is reflected in its low reactivity with non-metals and its

“noble” character. However, it is a metal and can be made to react with non-metals. Like

other transition metals it is found in multiple oxidations states, primarily the 0, 1+, and 3+

oxidation states.

In this lab you will explore the chemistry of gold in several different oxidation states.

You will begin with gold in the 3+ oxidation state in the form auric acid, HAuCl4. Auric acid is

obtained by dissolving the metal (0 oxidation state) in aqua regia (a mixture of nitric and

hydrochloric acids) and contains the complex ion [AuCl4]-. This complex is very hydroscopic

and you will use it as a solution in water.

As you might expect (why?), auric acid is a good oxidizing agent and is readily

reduced. In Part a of this experiment you will use a phosphine, Ph3P, to reduce and complex

the gold to make the Au(I) complex Ph3PAuCl (eq 1). A chloride ligand on a metal is very

useful as it can usually be replaced by other ligands to make new complexes. This is

HAuCl4 + 2Ph3P + H2O -------> Ph3PAuCl + Ph3P=O + 2HCl (1)

the case for Ph3PAuCl and in part b you will replace the chloride ligand with an oxo (O2-)
ligand to make the gold(I) oxo complex [(Ph3PAu)3(µ3-O)]BF4 (eq 2). The oxo

3Ph3PAuCl + Ag2O + NaBF4 --> [(Ph3PAu)3(µ3-O)]BF4 + 2AgCl + NaCl (2)

complex has the interesting structure shown below where the oxygen atom bridges the three

Au atoms of the complex ion [(Ph3PAu)3(µ3-O)]+. This is indicated in the formula by including

the µ3- before the oxygen.

Chemistry 141 Fall 2004

Me Me +
N
-
N BF4
O +
Au Au
Au Au - Ph3P Au
BF4 PPh3
Ph3P Au
PPh3
Ph3P
Ph3P

[(Ph3PAu)3(µ3-O)]BF4 [(Ph3PAu)3(µ3-NNMe2)]BF4

In part c of this experiment you will use the use the oxo complex in a condensation reaction

with 1,1-dimethyl hydrazine according to eq 3. You will not isolate the resulting

[(Ph3PAu)3(µ3-O)]BF4 + Me2NNH2 --> [(Ph3PAu)3(µ3-NNMe2)]BF4 + H2O (3)

hydrazido complex [(Ph3PAu)3(µ3-NNMe2)]BF4 (see structure above) but will decompose it in

solution according to eq 4.

2[(Ph3PAu)3(µ3-NNMe2)]BF4 --> [(Ph3PAu)6](BF4)2 + Me2NN-NNMe2 (4)

You will then isolate the gold cluster complex [(Ph3PAu)6](BF4)2. Look carefully at the
structure of this complex given below and note some unusual features.

2+
Ph3P PPh3
PPh3
Au Au
Au
-
2BF4
Au
Au Au
PPh3 PPh3
Ph3P

[(Ph3PAu)6](BF4)2
Chemistry 141 Fall 2004

1. This complex is held together by Au-Au bonds. This is why it is called a cluster. It is

a cluster or group of Au atoms bonded to each other. The geometry of this cluster is

an edge-shared bi-tetrahedron.

2. What is the oxidation state of the gold in this complex? The complex ion

[(Ph3PAu)6]2+ has a 2+ charge. The Ph3P ligands are related to ammonia and are

neutral so that the 2+ charge must be shared by the six gold atoms. Each gold atom

must therefore have an average oxidation number of +2/6 or +1/3! Another way to

look at this is to assign two of the gold atoms an oxidation number of +1 and the

remaining 4 an oxidation number of 0, the same oxidation number as metallic gold!

This complex is like a little piece of the metal surrounded by ligands.

There are many more gold cluster complexes similar to [(Ph3PAu)6]2+. The largest that is still

considered a molecule has 55 gold atoms in it. Larger ones are also known with thousands of

Au atoms in them but these are no longer considered to be molecules but small metal

particles (colloids). These are finding many important applications in areas as diverse as

nano-electronics and DNA identification. Clusters of gold, other metals, and mixtures of

metals have been studied for many years as models for catalyst that are used in many

important reactions such as occur in the catalytic converter on automobiles. This is an active

and growing area of chemistry.

Experimental Procedure

Caution: 1,1-dimethyl hydrazine (see part c) is a cancer suspect agent. Use with caution in

the hood and wear gloves.

Caution: Do not get the auric acid on your skin. It will leave a purple stain of finally divided
Chemistry 141 Fall 2004

gold. (Gold Finger?) Though unsightly, the stain is harmless and will wear off after a few

days. The same goes for the silver nitrate but the stain will be black.

Note: Gold can be easily recycled so please put all gold containing materials in the

designated container.

a. Synthesis of Ph3PAuCl. Ph3P (1.10 g, 4.20 mmol), dissolved in 10 mL of ethanol,

is slowly added to a stirred solution of HAuCl4 (2.00 mmol, from 8.00 mL of a 0.25 M aqueous

solution) in ethanol (15 mL) at 0˚C. The mixture is warmed to room temperature with

continued stirring. The initial yellow precipitate turns white. The white product is isolated by

filtration, washed with ethanol, and dried in vacuo.

b. Synthesis of [(Ph3PAu)3(µ3-O)]BF4. In a 50 mL round bottom flask, silver nitrate

(0.8 g, 4.7 mmol) is dissolved in 20 mL of distilled water and a 50% NaOH solution is added

drop-wise until no further precipitate forms. (This takes about 12 drops. Swirl the flask

between each drop and allow the precipitate to settle before adding the last few drops so that

you can see if any more precipitate forms.) The brown precipitate of Ag2O is allowed to settle.

The supernatant is decanted and the solid is washed successively with water (3 x 5 mL),

ethanol (2 x 5 mL), and acetone (2 x 5 mL), at each wash decanting-off as much of the wash
liquid as you can without losing the bulk of the solid. Acetone (20 mL), NaBF4 (0.8 g, 7

mmol), and Ph3PAuCl (0.64 g, 1.3 mmol) is then added to the freshly prepared Ag2O. After
vigorous stirring for 1 hour, the acetone is removed under reduced pressure and the residue

is extracted with CH2Cl2 (3 x 5 mL). The combined CH2Cl2 extract is filtered with Celite,

reduced to a few mL, and THF (~40 mL) is slowly added to the solution. White crystals should

slowly appear at this time. After standing for 10 min, the mixture is swirled and the white

crystalline product is filtered off, washed with ether, and dried in vacuo.
Chemistry 141 Fall 2004

c. Synthesis of [(Ph3PAu)6](BF4)2. The oxo complex (0.20 g, 0.14 mmoles) is

dissolved in 5 mL of CH2Cl2 and 0.5 mL of a 0.30 M solution of 1,1-dimethyl hydrazine is

added with stirring. The reaction flask is then fitted with a condenser and the mixture is

heated at reflux for 30 min. After the mixture has cooled to room temperature, the volume is

reduced to 1 or 2 mL and ether (~15 mL) is slowly added to precipitated the green-brown

product, which is filtered off, washed with ether, and dried.

Congratulations for making it this far!

Characterize all three products by 31P NMR spectroscopy in CH2Cl2.

Please respond to the following.

1. Consider the reaction in eq 1.

a. Write half-reactions (oxidation and reduction).

b. What is the reducing agent and what is the oxidizing agent.

c. What elements change oxidation numbers and by how much?

2. Repeat the above for the reaction given in eq 4.

3. What is the d-electron count for the gold complexes in eq 1-3?

4. Explain the color change on going from HAuCl4 (orange) to Ph3PAuCl (white).
31
5. Does the P NMR spectrum of the cluster [(Ph3PAu)6](BF4)2 match the geometry given

above? Can you explain why it might not? (Hint: If the NMR spectrum is recorded at –100 oC

two peaks are observed in the ratio 2:1.)

6. Give a balanced eq for the formation of silver oxide.