4198
C.-K. Li et al. / Inorganica Chimica Acta 358 (2005) 4191–4200
P Æ 1/2(CH3)2CO: C, 46.26; H, 4.52. Found: C, 45.98; H,
4.29%.
4.5. Crystal structure determination
Single crystals of 2 suitable for X-ray diffraction stud-
ies were grown by layering n-hexane onto a dichloro-
methane and acetone solution of the corresponding
complexes, respectively. The sodium ion-bound form
of 3 was obtained by using the sodium salt of diet-
hyldithiocarbamate in the preparation of the complex
instead of diethylammonium diethyldithiocarbamate,
and the crystals of 3 Æ NaPF6 suitable for X-ray diffrac-
tion studies were grown by slow evaporation of a dichlo-
romethane–n-hexane (ca. 10:1 v/v) solution of the
complex.
4.4.2. [Au2(l-i-mnt)(Ph2P-b15c5)2] (2)
To a stirred solution of 1 (100 mg, 0.15 mmol) in
dichloromethane (5 ml) was added (Et4N)2[i-mnt] (29
mg, 0.073 mmol). The solution immediately turned yel-
low. The reaction mixture was stirred for 3 h at room
temperature, after which the solvent was removed under
reduced pressure, and the yellow residue was dissolved
in acetone. Filtration followed by subsequent recrystal-
lization from acetone–hexane gave yellow crystals of 2
1
(75 mg, 0.052 mmol, 70% yield). H NMR (300 MHz,
CDCl3, 298 K): d 3.75 (m, 16H, –OCH2–), 3.80 (t, 4H,
J = 3.6 Hz, –C6H3OCH2CH2–), 3.91 (t, 4H, J = 4.1
Hz, –C6H3OCH2CH2–), 4.03 (t, 4H, J = 4.2 Hz,
–C6H3OCH2–), 4.15 (t, 4H, J = 4.2 Hz, –C6H3OCH2–),
6.82 (dd, 2H, J = 2.9, 8.1 Hz, aryl H meta to P), 6.95–
7.00 (m, 2H, aryl H ortho to P), 7.16 (dd, 2H, J = 1.6,
14.1 Hz, aryl H ortho to P), 7.30–7.45 (m, 20H, –
PPh2). 31P{1H} NMR (202 MHz, CDCl3, 298 K): d
36.2 (s). Positive-ion FAB mass spectrum: m/z 1439
[M + H]+. IR (Nujol mull on KBr disc, m/cmꢀ1): 2203
m(C ” N). Elemental Anal. Calc. for C56H58Au2-
N2O10P2S2: C, 46.74; H, 4.06; N, 1.95. Found: C,
46.55; H, 4.05; N, 1.89%.
4.5.1. [Au2(l-i-mnt)(Ph2P-b15c5)2] (2)
[C56H58Au2N2O10P2S2 Æ 2(CH3)2CO]; formula wei-
˚
A,
ght = 1553.18,
triclinic,
P1,
a = 12.397(3)
˚
˚
b = 13.702(3) A, c = 20.474(4) A, a = 105.64(3)ꢁ, b =
3
˚
107.58(3)ꢁ, c = 93.92(3)ꢁ, V = 3149.8(11) A , Z = 2,
Dc = 1.638 g cmꢀ3, l (Mo Ka) = 4.830 mmꢀ1, F(000) =
1540, T = 293 K.
A
crystal of dimensions
0.4 · 0.15 · 0.08 mm mounted in a glass capillary was
used for data collection at 20 ꢁC on a MAR diffractom-
eter with a 300 mm image plate detector using graphite
˚
monochromatized Mo Ka radiation (k = 0.71073 A).
Data collection was made with 2ꢁ oscillation step of u,
300 s exposure time and scanner distance at 120 mm.
Hundred images were collected. The images were inter-
preted and intensities integrated using program DENZO
[20]. The structure was solved by direct methods
employing SIR-97 program [21] on PC. Gold, sulfur,
phosphorus and many non-hydrogen atoms were lo-
cated according to the direct methods and the successive
least-squares Fourier cycles. Positions of other non-
hydrogen atoms were found after successful refinement
by full-matrix least squares using program SHELXL-97
[22] on PC. Two acetone solvent molecules were also lo-
cated. The ꢀend-siteꢁ of crown ethers were found to have
high thermal parameters and C(30) was treated to be
disordered into two positions. Atoms of C(29), C(31),
C(32) and O(8) were refined isotropically. For conver-
gence of least-squares refinements, restraints were ap-
plied to these atoms, assuming similar corresponding
1,2- and 1,3-bond lengths or distances, i.e., the pairs of
C(29)–C(30) and C(29)–C(300); C(31)–C(30) and
C(31)–C(300); O(9)ꢁ ꢁ ꢁC(31), O(8)ꢁ ꢁ ꢁC(29), O(7)ꢁ ꢁ ꢁC(30)
and O(7)ꢁ ꢁ ꢁC(300); O(8)–C(30) and O(8)ꢁ ꢁ ꢁC(300);
O(9)–C(32) and O(8)–C(31), respectively. The same
thermal parameters were also assumed for the disor-
dered atoms. According to the SHELXL-97 program
[22], all 10488 independent reflections (Rint equal to
0.0346, 6722 reflections larger than 4r(Fo), where
Rint ¼ RjF 2o ꢀ F o2ðmeanÞj=R½F 2oꢂ) from a total 21194
reflections were participated in the full-matrix least-
squares refinement against F2. These reflections were in
the range ꢀ14 6 h 6 14, ꢀ15 6 k 6 15, ꢀ24 6 l 6 24
4.4.3. [Au2(l-dtc)(Ph2P-b15c5)2](PF6) (3)
To a stirred solution of 1 (100 mg, 0.15 mmol) in
dichloromethane (5 ml) was added solid AgOTf (40
mg, 0.15 mmol). Stirring was continued for 30 min in
the dark, and the grey precipitate of silver chloride
was then filtered. To the clear colorless filtrate was then
added (Et2NH2)[dtc] (16 mg, 0.073 mmol), and the solu-
tion immediately turned yellow. The reaction mixture
was stirred at room temperature for 1 h. The yellow
solution was filtered, and the solvent was removed under
reduced pressure. The yellow residue was dissolved in
methanol. Metathesis reaction with saturated ammo-
nium hexafluorophosphate solution in methanol gave
the product as a yellow solid. Subsequent recrystalliza-
tion from diffusion of diethyl ether into a dichlorometh-
ane–acetonitrile (10:1 v/v) mixture of the crude product
gave yellow crystals of 3 (77 mg, 0.049 mmol, 65%
yield). 1H NMR (300 MHz, CDCl3, 298 K): d 1.50
(t, 6H, J = 7.40 Hz, –CH3), 3.60 (m, 16H, –OCH2–),
3.85 (m, 8H, –C6H3OCH2CH2–), 3.90 (m, 4H,
–C6H3OCH2–), 4.01 (m, 4H, –C6H3OCH2–), 4.10 (q,
4H, J = 7.00 Hz, –CH2–), 6.50 (dd, 2H, J = 2.4, 8.1
Hz, aryl H meta to P), 6.80 (m, 4H, aryl H ortho to
P), 7.50–7.75 (m, 20H, –PPh2). 31P{1H} NMR (202
MHz, CDCl3, 298 K): d 38.2 (s). Positive-ion FAB mass
spectrum: m/z 1447 [M ꢀ PF6]+. Elemental Anal. Calc.
for C57H68Au2F6NO10P3S2 Æ 4CH2Cl2 Æ CH3CN: C,
38.35; H, 4.04; N, 1.42. Found: C, 38.49; H, 4.08; N,
1.40%.