2534
S. Ito et al. / Journal of Organometallic Chemistry 690 (2005) 2531–2535
3
˚
other hand, the p-allylpalladium(II) complex 15 was
useful for the direct conversion of allyl alcohol. The
V = 1576.7(2) A , Z = 2, 2h
= 55.0°, T = 296 K,
max
À1
À1
q = 1.164 g cm , l = 0.289 mm , 12608 collected
reflections, 4305 unique reflections (Rint = 0.042),
1
,3-diphosphapropene derivatives could be widely em-
ployed as a novel ligand system of metal complexes.
Compound 5, generated through sulfurization of 2,
was structurally characterized and expected to function
as a novel S2-ligand.
R1 = 0.081 (I > 2r(I)), R = 0.095 (all data), S = 1.70
w
(325 parameters). Crystallographic data (excluding
structure factors) for the structure have been deposited
with the Cambridge Crystallographic Date Centre as
supplementary publication number CCDC-242211.
Copies of the data can be obtained free of charge on
application to CCDC, 12 Union Road, Cambridge
CB2 1EZ UK [fax: +44(0)-1223-336033 or e-mail:
deposit@ccdc.cam.ac.uk.
4
. Experimental section
4
.1. Preparation of 4 and 5
4
.3. The sonogashira coupling with 14
A solution of 2 (0.720 g, 1.47 mmol) and sulfur (4.5
mmol as S) in toluene (25 mL) was refluxed for 24 h.
The solution was allowed to cool to room temperature
and the solvent was removed in vacuo. Compounds 4
and 5 were obtained after silica gel column chroma-
tography (hexane/AcOEt 20:1) of the residue. 4: 0.40
g (52% yield); the physical data were identical to
our previous report [9]. 5: 0.10 g (12% yield); Color-
Complex 14 was prepared according to [9]. A mixture
of iodobenzene (1.0 mmol), phenylacetylene (1.0 mmol),
4 (0.025 mmol), copper(I) iodide (0.025 mmol), and tri-
ethylamine (4 mL) was stirred under argon at room tem-
perature for 4 h. The solvent was removed in vacuo and
the residue was extracted with ether. The solution was
concentrated and the residue was chromatographed over
silica gel (hexane) to afford 0.18 g of diphenylacetylene
1
31
1
less prisms (hexane) m.p. 185–188 °C;
P{ H}
NMR (162 MHz, CDCl ): d 188.6 [P(S)@C], 46.2
3
(99% yield).
2
1
[
P(Ph )@S], JPP = 21 Hz; H NMR (400 MHz,
CDCl ): d 8.06 (m, 4H, Ph), 7.56 (d, J = 2.2 Hz,
2
4
3
PH
4
.4. The suzuki coupling with 14
2
Bu), 1.57 (dd, JPH = 11.2 Hz,
H, Mes*), 7.52–7.48 (m, 6H, Ph), 1.69 (s, 18H, o-t-
3
3
J
C{ H} NMR (101
= 3.5 Hz, 3H,
PH
A solution of iodobenzene (2.00 mmol), phenylboric
acid (3.00 mmol), 14 (0.080 mmol), potassium carbonate
6.00 mmol) in THF (10 mL) was refluxed for 20 h and
1
3
1
CH ), 1.32 (s, 9H, p-t-Bu);
3
4
MHz, CDCl ): d 154.6 (d, JPC = 3.5 Hz, p-Mes*),
1
2
3
2
(
53.8 (d,
JPC = 10.3 Hz, o-Ph), 131.8 (d,
JPC = 7.1 Hz, o-Mes*), 132.6 (d,
3
after being allowed to cool to room temperature 10 mL
of ether and 10 mL of water were added. The extracted
organic layer was dried over MgSO . The solution was
JPC = 2.9 Hz, p-
Ph), 128.7 (d, JPC = 12.9 Hz, m-Ph), 133.1 (dd,
3
1
3
JPC = 88.3 Hz, JPC = 3.2 Hz, ipso-Ph), 132.5 (d,
4
concentrated and silica gel column chromatography of
the residue (hexane) afforded 0.26 g of biphenyl (83%
yield based on iodomethane).
2
1
JPC = 10.7 Hz o-Ph), 125.7 (dd,
3
JPC = 72.3
Hz, JPC = 5.7 Hz, ipso-Mes*), 124.7 (d, JPC = 13.2
3
1
Hz, m-Mes*), 121.3 (dd, J = 101.9 Hz, J = 69.1
1
PC
PC
3
Hz, P@C), 39.9 (d, J = 2.6 Hz, o-CMe ), 35.7 (s,
PC
3
4
.5. Synthesis of allylanilines with 15
p-CMe ), 34.1 (s, o-CMe ), 31.4 (s, p-CMe ), 21.5 (d,
À1
3
3
3
2
JPC = 5.8 Hz, CH ); IR (KBr): m690, 652 cm
3
Complex 15 was prepared according to [9]. A solution
of allyl alcohol (1.00 mmol), aniline (2.00 mmol), 15
0.020 mmol), and MgSO (2.00 mmol) in toluene (3
(
S, 11.60%. Found: C, 69.24, H, 7.71, S, 11.88%.
P@S). Anal. Calc. for C H P S: C, 69.53; H, 7.66;
3
2
42 2
(
4
mL) was stirred at room temperature for 2 h. The solu-
tion was filtered through Celite and the filtrate was con-
centrated. The residual material was treated by silica gel
column chromatography (hexane/AcOEt) to afford 74
mg of allylaniline (63% yield) and 5.1 mg of bis(allyl)an-
iline (3% yield).
4
.2. X-ray crystallography of 5
X-ray diffraction data were collected on a Rigaku
RAXIS-IV imaging plate diffractometer. The structure
was solved by direct methods (SIR92) [15] and expanded
using Fourier techniques (DIRDIF94) [16]. The non-hy-
drogen atoms were refined anisotropically. The hydro-
gen atoms were put on the calculated positions.
Structure solution, refinement, and graphical represen-
tation were carried out using the teXsan package [17].
Crystal data of 5: C H P S , M = 552.75, triclinic,
Acknowledgements
This work was supported in part by Grants-in-Aid
for Scientific Research (No. 13304049 and 14044012)
from the Ministry of Education, Culture, Sports, Sci-
ence and Technology, Japan. H. Liang is grateful to
3
2
42 2 5
ꢀ
P1 (#2), a = 10.6640(2), b = 16.0652(9), c = 10.6455(7)
˚
A, a = 104.276(4), b = 115.560(2), c = 76.308(1)°,