242
N. Nasser, R.J. Puddephatt / Inorganica Chimica Acta 409 (2014) 238–243
Table 1
Crystal and refinement data.
Complex
dpppi
22H18NO2.13
dpppa
1ꢁCH2Cl2
2
Formula
C
P
C36H34N2O2P2
588.59
monoclinic
P21/c
11.8968(9)
27.634(2)
9.5537(8)
90
98.554(5)
90
3105.9(4)
4
C37H36Au2Cl4N2O2P2
1138.35
monoclinic
C2/c
33.585(9)
12.155(3)
9.658(2)
90
93.540(10)
90
3935.0(17)
4
C40H34Ag2F6N2O6P2
1030.37
triclinic
Formula weight
Crystal system
Space group
a (Å)
b (Å)
c (Å)
361.42
triclinic
ꢀ
ꢀ
P1
P1
9.364(2)
10.099(2)
11.111(3)
63.414(9)
76.315(10)
71.406(11)
885.1(4)
2
11.128(3)
13.002(4)
15.233(4)
72.428(12)
74.971(11)
78.552(10)
2011.8(10)
2
a
(°)
b (°)
c
(°)
V (Å3)
Z
T (K)
110(2)
1.356
110(2)
1.259
110(2)
1.922
110(2)
1.701
dcalc (Mg mꢀ3
)
l
k
0.172
0.175
7.836
1.130
0.71073
14506/320
0.044
0.71073
5284/379
0.060
0.71073
7403/223
0.043
0.71073
23760/523
0.042
Reflection/parameter
R1(I > 2 I)
wR2(all)
r
0.1363
0.153
0.093
0.100
chemical shifts are reported relative to TMS (1H), 85% H3PO4. Mass
spectrometric analysis was carried out using an electrospray PE-
Sciex Mass Spectrometer (ESI-MS) coupled with TOF detector.
X-ray crystallography [29]. A suitable crystal of each compound
was coated in Paratone oil and mounted on a glass fiber loop. X-ray
73.53; H, 5.05; N, 3.90. Found: C, 73.60; H, 5.11; N, 4.06%. Single
crystals of dpppi, which co-crystallized with some phosphine oxide
[d(31P) = 28.63, s], were obtained by the slow evaporation of a solu-
tion of the compound dissolved in ethyl acetate. Data for dpppa:
yield 0.35 g, 40%. NMR in CDCl3: d(1H) = 7.25–7.43 [m, 24H, Ph
and C6H4]; 6.89 [m, 2H, J = 5, 2 Hz, NH]; 3.46 [m, 4H, CH2N]; 2.31
[m, 4H, CH2P]; d (31P) = ꢀ21.29 [s]. ESI-MS: m/z = 588.1. Calc.
588.2. Single crystals of dpppa were grown by slow diffusion of
n-pentane into a solution of the compound dissolved in chloro-
form. Anal. Calc. for C36H34N2O2P2: C, 73.46; H, 5.82; N, 4.76.
Found: C, 73.33; H, 5.98; N, 4.56%.
data were collected at 150 K with
x and u scans using a Bruker
Smart Apex II diffractometer and Bruker SMART software or Nonius
Kappa-CCD diffractometer with COLLECT software, using graph-
ite-monochromated Mo K
a radiation (k = 0.71073 Å). Unit cell
parameters were calculated and refined from the full data set.
Reflections were scaled and corrected for absorption effects using
SADABS. All structures were solved by either Patterson or direct
methods with SHELXS and refined by full-matrix least-square tech-
niques against F2 using SHELXL. All non-hydrogen atoms were re-
fined anistropically. No constraints were used. The hydrogen
atoms were placed in calculated positions and refined using the
riding model. Crystal data are summarized in Table 1 and in the
cif files. The compound dpppi exhibited a compositional disorder
in which the analogous phosphine oxide co-crystallized as an
impurity in the sample crystal. Alternative positions for the phos-
phorus (P10) and the oxygen (O30) were obtained from a difference
Fourier map. The occupancy of phosphine oxide moiety was re-
fined to a normalized value of 0.129(2). The molecule of complex
1 resides on a crystallographic 2-fold axis. There is a solvent CH2-
Cl2 molecule included in the lattice which also resides on the 2-fold
axis.
4.3. [Au2Cl2(dpppa)], 1
To a solution of dpppa (0.1 g, 0.170 mmol) dissolved in CH2Cl2
(10 mL) was added a solution of [AuCl(SMe2)] (0.10 g, 0.34 mmol)
in CH2Cl2 (5 mL). Upon addition, a colorless precipitate was formed
immediately. After allowing the reaction to stir for ca. 5 h., the sol-
vent was evaporated and the product was isolated, washed with
pentane (3x5 mL) and ether (3 ꢂ 5 mL) and dried under high vac-
uum. Yield: 0.15 g, 83%. NMR in DMSO-d6: d(1H) = 8.51 [br, 2H,
NH]; 7.28–7.87 [m, 24H, Ph and C6H4]; 3.43 [m, 4H, NCH2]; 2.97
[m, 4H, CH2P]; d(31P) = 24.86 [s]. Single crystals of complex 1ꢁCH2-
Cl2 were grown by slow diffusion of n-pentane into a solution of
the compound dissolved in dichloromethane, acetone, methanol,
dmso and chloroform (0.1 mL of each). Anal. Calc. for C37H36Au2Cl4-
N2O2P2: C, 39.04; H, 3.19; N, 2.46. Found: C, 39.02; H, 2.87; N,
2.54%.
4.2. 1,2-C6H4(CONHCH2CH2PPh2)2, dpppa, and 1,2-
C6H4(CO)2NCH2CH2PPh2, dpppi
To
a
solution of 2-(diphenylphosphinoethyl)amine (1.0 g,
4.4. [Ag2(OCOCF3)2(dpppa)], 2
4.36 mmol) and triethylamine (4 mL) in CHCl3 (10 mL) was added
dropwise a solution of phthaloyl dichloride (0.3 g, 1.45 mmol) in
CH2Cl2 (10 mL). After stirring for 12 h., the reaction mixture was
washed with water (3 x 30 mL), the organic layer was separated,
dried over MgSO4, then filtered, and the solvent was evaporated
under vacuum. The products were separated by column chroma-
tography. Elution with 30:70 EtOAc/hexane gave dpppi and then
elution with 60:40 EtOAc/hexane gave dpppa. The solvent was
evaporated to give dpppi or dpppa as a white solid, each of which
was dried under vacuum. Data for dpppi: yield 0.20 g, 38%; NMR in
CDCl3: d(1H) = 7.58–7.80 [m, 4H, C6H4]; 7.45–7.21 [m, 10H, Ph];
3.85 [m, 2H, NCH2]; 2.45 [m, 2H, CH2P]; d (31P) = ꢀ21.46 [s]. ESI-
MS: m/z = 359.2. Calc. 359.11. Anal. Calc. for C22H18NO2P: C,
To a stirred solution of dpppa (0.10 g, 0.170 mmol) in dry CH2-
Cl2 (15 mL) was added
a solution of silver trifluoroacetate
(0.075 g, 0.34 mmol) in THF (5 mL). After 10 h., the solvent was re-
moved under vacuum and a white solid was obtained which was
washed with pentane (3 ꢂ 2 mL) and ether (3x2 mL) and then
dried under high vacuum. Yield: 0.13 g, 75%. NMR in CD2Cl2:
d(1H) = 8.86 [br, 2 H, NH]; 7.78–7.30 [m, 24H, Ph and C6H4];
3.61[m, 4H, NCH2]; 2.68 [m, 4H, CH2P]; d(31P) = ꢀ2.65 [s]. Single
crystals of complex 2 were grown by slow diffusion of n-pentane
into a solution of the compound dissolved in dichloromethane
and chloroform. Anal. Calc. for C40H34Ag2F6N2O6P2: C, 46.63; H,
3.33; N, 2.72. Found: C, 46.37; H, 3.30; N, 2.88%.