Supporting Information

Instrumentation
Reactions were carried out in an Omnical Insight CPR 220 reaction calorimeter, in which the
instantaneous enthalpy balance around the vessel was continuously monitored. The sample
vessel was a 15 ml septum-cap vial, and the volume of the reactive solution was approximately 5
ml.

Materials
Anhydrous toluene was purchased from Aldrich. The sodium-tert-butoxide (Aldrich) was stored
in a glove box and vacuum dried for at least 12 hours prior to use; the benzophenone hydrazone
(Acros) was stored in a fridge and used without further purification. Hexylamine (Aldrich),
tridecane (Aldrich), palladium acetate (Sigma-Aldrich) and BINAP (Aldrich) were used as
received.

Standard conditions (Figure 1)

Reaction between benzophenone hydrazone and 3-bromobenzotrifluoride: quantities
Palladium acetate (10.1 mg, 0,045 mmol), BINAP (37.4 mg, 0.06 mmol), sodium-tert-butoxide
(216.2 mg, 2.25 mmol), benzophenone hydrazone (392.5 mg, 2 mmol), tridecane (151.2 mg,
0.820 mmol) as the internal standard, 3-bromobenzotrifluoride (462.4 mg, 2.05 mmol), toluene
(4.5ml). The heat of reaction was approximately 147 KJ/mol ( 2 KJ/mol).

S1

Reaction between hexylamine and 3-bromobenzotrifluoride: quantities

Palladium acetate (10.1 mg, 0,045 mmol), BINAP (37.3 mg, 0.06 mmol), sodium-tert-butoxide
(216.2 mg, 2.25 mmol), hexylamine (201.6 mg, 1.99 mmol), tridecane (151.2 mg, 0.820 mmol)
as the internal standard, 3-bromobenzotrifluoride (462.4 mg, 2.05 mmol), toluene (4.46 ml). The
heat of reaction was approximately 205 KJ/mol ( 9 KJ/mol).

All the components except the aryl halide were added in a standard vial and then placed in the
calorimeter, which had been previously heated to 90C.

The thermically equilibrated 3-

bromobenzotrifluoride was injected to the thermically equilibrated reaction mixture after

approximately 60 minutes (this time was necessary in order to obtain a stable signal from the
calorimeter). The final conversion was measured by GC on a quenched sample.

Sampling experiment (Figure 2)

In the sampling experiments, reactions were carried out at the same conditions as previously
described; samples were taken at regular intervals, quenched in water/toluene mixture at ambient
temperature and analyzed by GC.
For the benzophenone reaction the conversion was calculated based on the benzophenone
hydrazone, using the equation: X Benz =

n0Benz n Benz
n0Benz

; on the contrary, for the hexylamine

reaction, the conversion was calculated based on the product, as in the following equation:

Hexyl

n Hexyla min e

product

n0Hexyla min e

S2

Subtraction of the heat of mixing

No subtraction of the heat of mixing was performed for the hexylamine reaction, as it is
negligible. On the contrary the heat of mixing was subtracted from the benzophenone hydrazone
reaction, as explained in the section below.
The heat profile of the reaction between benzophenone hydrazone and 3-bromobenzotrifluoride
(at standard conditions previously described) is shown in Figure S1.
180
160

Heat (mW)

140
120
100
80
60
40
20
0
0

10

20

30

40

50

Time (min)
Figure S1: Heat profile of a reaction between benzophenone hydrazone (initial concentration 0,4M) and 3bromobenzotrifluoride (0,4M), at 90C.

We remember that, in this experiment, we inject 3-bromobenzotrifluoride, at time=0, to a

solution containing all the other components involved in the reaction. The bump which can be
clearly seen at the beginning of the graph refers to the heat of mixing generated by this injection.
In order to obtain a heat curve which represents only the heat of reaction, we had to subtract this
heat of mixing. We therefore carried out a very similar experiment in the calorimeter, employing
the same exact technique, conditions and concentrations, except for the palladium acetate, which
was not added to the solution. As a consequence, without the catalyst, the reaction could not take
place, and we could calculate precisely the heat generated by the injection of the aryl halide,
which is shown in Figure S2.

S3

70

Heat (mW)

60
50
40
30
20
10
0
0

Time (min)

Figure S2: Heat of mixing generated by injecting 3-bromobenzotrilfuoride to a solution of toluene containing
benzophenone hydrazone, tridecane and sodium-tert-butoxide, at 90C.

By subtracting the heat curve represented in Figure S2 from the heat curve represented in Figure
S1, we could obtain the heat profile as shown in Figure 1a.

S4