I. Bustos, et al.
Inorganica Chimica Acta 498 (2019) 119165
4
.3. Preparation of [IrCl(PPh
2
(o-C
6
H
4
CO))
2
(NH
2
(CH
2
)C
4
H
3
O)] (3)
Table 2
Crystal data and structure refinement for compounds 2, 3 and 4.
Furfurylamine (0.078 mmol, 6.9 µL) was added to a suspension of
Crystal Data
2
3
4
[
IrHCl{(PPh
2
(ο-C
6
H
4
CO)) H}] (0.037 mmol, 30 mg) in methanol. The
2
Empirical
formula
Formula weight
CCDC number
Temperature K
Crystal system
Space group
a/Å
C
49
H
50
3
N O
P
5 2
Ir
C
44
H
4
39ClNO P
2
Ir
C
44
H
3 2 2
37Cl NO P Ir
suspension was heated to reflux for 5 h and a yellow solution was ob-
tained. It was left to cool down and a yellow solid appeared. The sus-
pension was centrifuged and the yellow solid was dried under vacuum
and recrystallised from methanol. Data: Yield 54% (18.5 mg). IR (KBr,
1015.06
935.35
1944025
100 (2)
Triclinic
P-1
972.23
1944023
100 (2)
Triclinic
P-1
1944024
100 (2)
Triclinic
P-1
−
1
cm ): 3297 (w, N–H); 1625 (s, C]O). Anal. Calcd. for
IrC43
H
35
P
2
O NCl: C 57.17, H 3.90, N 1.55; found C 57.18, H 3.89, N
3
1
11.1557(5)
11.3357(6)
10.4310(12)
10.5830(17)
18.558(2)
93.039(4)
104.688(4)
105.298(4)
1895.6(4)
2
13.5694(5)
18.0658(7)
18.2342(7)
70.1540(10)
75.8030(10)
88.8330(10)
4066.4(3)
4
1
.62. H NMR (CDCl
3
): δ 3.23 (m, 1H, H
2
N); 5.66 (m, 1H, H
2
2
N); 2.44 (t,
C); 5.73 (s,
b /Å
3
3
J
H,H = 12.4 Hz, 1H, H
2
C); 3.57 (t,
J
H,H = 13.2 Hz, 1H, H
c/Å
18.0363(10)
75.347(2)
81.565(2)
89.839(2)
2181.38(19)
2
1
H, HC-C); 6.12 (s, 1H, HC-CH); 7.15 (s, 1H, HC-O); 6.40–8.30 (28H,
α/°
3
1
1
2
Aromatics) ppm. P{ H} NMR (CDCl
3
): δ 9.3(d, JP,P = 5 Hz); 22.3 (d,
β/°
2
13
1
γ/°
J
P,P = 5 Hz) ppm. C{ H} NMR (CDCl
3
): δ 41.4 (s, CH ); 107.4 (s, CH-
2
3
Volume (Å )
C); 110.1 (s, CH-CH); 142.1 (s, CH-O); 124.0–134.5 (Aromatics); 208.3
Z
2
P,C = 8 Hz, C]O); 231.0 (d, 2
(
d,
J
J
P,C = 108 Hz, C]O) ppm.
D(calcd), g cm−3
1.545
1.639
1.588
μ(MoKα)
3.185
3.722
3.597
mm 1)
−
(
4
.4. Preparation of [IrH(PPh
2
(o-C
6
H
4
CO)(PPh
2
(o-C
6
H C]N
4
Parameters
455
479
901
(
CH )C O))] (4)
2
H
4 3
GOF
1.082
1.064
1.086
a,b
R
1
0.0190 (10610)
0.0465 (11382)
0.527 and −1.096
0.0171 (9252)
0.0397 (9857)
0.0312 (16170)
0.0754 (20205)
c
Furfurylamine (0.096 mmol, 8.5 µL) was added to a tetrahydrofuran
Rw
2
suspension of [IrHCl{(PPh
2
(ο-C
6
H
4
CO))
2
H}] (0.037 mmol, 30 mg) and
Largest diff. in
peak and
0.794 and −0.359
1.253 and −2.003
it was stirred for 120 h (5 days). The volume was reduced and hexane
was added until a yellow solid precipitated. The solid was centrifuged,
dried under vacuum and recrystallised from dichloromethane/diethyl
−
3
hole e Ả
a
b
c
Σ ||F
o
| − |F
c
||/Σ|F |.
o
−
1
ether. Data: Yield 46% (15 mg). IR (KBr, cm ): 2184 (s, Ir-H); 1550 (s,
Values in parentheses for reflections with I < 2σ(I).
{Σ[w(Fo2 − F ) ]/Σ[w(F ) ]}
2 2 2 2 1/2
.
C]O and C]N). Anal. Calcd. for IrC43
H
35
P
2
O
2
NCl: C 58.20, H 3.98, N
): δ −20.50 (t,
C); 6.50 (s, 1H,
c
o
1
1
.58; found C 57.83, H 4.28, N 1.57. H NMR (CDCl
3
2
2
3
J
P,H = 14 Hz, 1H, H-Ir); 5.2 (d,
J
H,H = 8 Hz, 2H, H
(λ = 0.71073 Å), operating at 50 kV and a temperature of 100 K. The
cell parameters were determined and refined by least-squares fit of all
reflections collected. In four cases, an empirical absorption correction
was applied. The data reduction was performed with the APEX2 [31]
software and corrected for absorption using SADABS [32]. Crystal
structures were solved by direct methods using the SIR97 program [33]
HC-C); 6.40 (s, 1H, HC-CH); 7.4 (s, 1H, HC-O); 6.8–8.3 (28H,
3
1
1
Aromatics) 13.4 (br, 1H, O–H–N) ppm. P{ H} NMR (CDCl
3
): δ 14.8(d,
P,P = 7 Hz); 29.8 (d, JP,P = 7 Hz) ppm. C{ H} NMR (CDCl ): δ 47.7
); 109.0 (s, CH-C); 110.0 (s, CH-CH); 142.8 (s, CH-O);
2
2
13
1
J
3
(
s, CH
2
2
1
23.0–135.5 (Aromatics); 223.0 (d,
J
P,C = 102 Hz, C]O or C]N);
43.0 (d, 2
J
P,C = 105 Hz, C]O or C]N) ppm.
and refined by full-matrix least-squares on F including all reflections
2
2
using anisotropic displacement parameters by means of the WINGX
crystallographic package [34]. In all cases, the hydrogen atoms were
included with at their calculated positions determined by molecular
geometry and refined riding on the corresponding bonded atom, except
for the hydride atoms bonded to Ir atoms in compounds 2 and 4, which
were located from the Fourier map and included. Several crystals of
compounds 2 and 4 were measured and the structures were solved from
the best data we were able to collect. Attempts to solve disorder pro-
blems with two dimethylformamide solvent molecules and one di-
chloromethane crystallization molecule failed in compounds 2 and 4,
4
.5. Catalytic studies
A typical hydrolysis experiment of amine-boranes is described
below. THF/H O = 60/40 mixtures, being the total volume 3 mL, and
2
0
.5 mol% catalyst loading were used; a solution of 1.38 mmol of amine-
borane in 1.2 mL of H O was prepared in a round bottom 40 mL flask
2
fitted with a gas outlet and with a side arm sealed with a septum cap.
The flask was connected via the gas outlet to a gas burette filled with
water. A solution of 0.007 mmol of the selected precatalyst in 1.8 mL of
dry THF was syringed through the septum while the magnetic stirring
was on and the timing started. Gas evolution began and the released
volume was measured by the volume of water displaced in the burette.
Volumes were measured at atmospheric pressure in the 20–40 °C range.
For the recyclability study of 2 the first hydrolysis reaction was done
as mentioned above. The successive ones were measured by adding
2
respectively. Instead, a new set of F (hkl) values with the contribution
from solvent molecules withdrawn was obtained by the use of the mask
2
tool implemented in OLEX2 [35]. Final R(F), wR(F ) and goodness of fit
agreement factors, details on the data collection and analysis can be
found in Table 2. CCDC 1944023–1944025 contain the supplementary
crystallographic data for this paper. These data can be obtained free of
1
.38 mmol of amine-borane dissolved in THF/H O = 60/40 (3 mL)
2
each time, maintaining the initial ratio of solvents but increasing the
volume in the flask.
The homogeneity test was performed by adding seventy times more
Hg moles than that of the precatalyst; for this, the reaction was pre-
pared as described above and the mercury (0.49 mmol, 7.2 µL) was
syringed through the septum at the beginning of the catalysis.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
4.6. X-ray crystallography
Prismatic yellow light crystals of compounds 2, 3 and 4 suitable for
Acknowledgements
X-ray experiments were obtained. In all cases a crystal was resin epoxy
coated and mounted on a Bruker D8 Venture with Photon detector
This research was supported by the Universidad del Pais Vasco
(UPV/EHU) (GIU 16/25 and EHUA16/32), Ministerio de Economia y
equipped
with
graphite
monochromated
MoKα
radiation
6