118
K.-H. Yih et al. / Journal of Organometallic Chemistry 665 (2003) 114ꢁ121
/
with dppe in CH2Cl2 at room temperature to give a
mixture of dinuclear dppe bridged complex [W(h3-
C3H5)(CO)2{h2-S2P(OEt)2}]2(m-dppe) (4) and [W(h3-
C3H5)(CO)2{h2-S2P(OEt)2}(h1-dppe)] (5). The vari-
able-temperature 1H-NMR experiments were used to
confirm the intramolecular trigonal twist rotational
behavior of 3 in the solution state.
(3). IR (CH3CN) y (CO) 1936(vs), 1840(vs); (KBr) y
(CO) 1916(vs), 1824(vs) cmꢃ1 31P{1H}-NMR (202
.
1
MHz, CDCl3, 298 K): d 108.9. H-NMR (500 MHz,
CDCl3, 298 K): d 1.41 (t, 3J(HH) 7.1 Hz, 6H,
OCH2CH3), 1.52 (d, J(HH) 8.9 Hz, 2H, Hanti of allyl),
2.32 (s, 3H, CH3CN), 3.06 (br, 2H, Hsyn of allyl), 3.35
(m, 1H, CH of allyl), 4.44 (q, J(HH) 7.1 Hz, 4H,
OCH2). 13C{1H}-NMR (125MHz, CDCl3, 298K): d 3.3
(s, CH3CN), 15.8 (s, OCH2CH3), 56.7 (s, CHꢁ
63.9 (s, OCH2), 75.5 (s, CH2ꢁCH), 119.5 (s, CH3CN),
220.0 (s, CO). MS (FAB, NBA): m/z 507 [Mꢂ], 466
[MꢂꢃCH3CN], 425 [Mꢂꢃ
CH3CNꢃC3H5], 397
[Mꢂꢃ CO], 369 [Mꢂꢃ
CH3CNꢃC3H5ꢃ CH3CNꢃ
C3H5ꢃ2CO]. Anal. Calc. for C11H18NO4PS2W: C,
/
CH2),
3. Experimental
/
3.1. Materials
/
/
/
/
/
/
/
/
All manipulations were performed under nitrogen
using vacuum-line, drybox, and standard Schlenk tech-
niques. NMR spectra were recorded on an AM-500 WB
FT-NMR spectrometer and are reported in units of d
(ppm) with residual protons in the solvent as an internal
standard (CDCl3, d 7.24; CD3CN, d 1.93; C6D6, d 7.15;
C2D6CO, d 2.04). IR spectra were measured on a
Nicolate Avator-320 instrument and were referenced
to a polystyrene standard, using cells equipped with
calcium fluoride windows. Mass spectra were recorded
on a JEOL SX-102A spectrometer. Solvents were dried
and deoxygenated by refluxing over the appropriate
reagents before use. n-Hexane, diethyl ether, THF and
/
26.04; H, 3.58; N, 2.76. Found: C, 26.34; H, 3.72; N,
2.98%.
3.3. Bis-[(h3-Allyl)(dicarbonyl)(h2-
diethyldithiophosphato)tungsten(II)] [m-bis-{(diphenylꢀ
/
phosphine)ethane} (4)
3.3.1. Method A
Two milliliter CH2Cl2 solution of dppe (0.396 g, 1.0
mmol) was added to a flask containing a solution of 3
(0.523 g, 1.0 mmol) in MeCN (20 ml). After stirring for
10 min, a yellowꢁ
precipitate was collected by filtration (G4) washed with
n-hexane (2ꢄ10 ml) and then dried in vacuo yielding
0.70 g (51%) of 4 and 0.17 g (19%) of 5. Recrystalliza-
tions using a mixture of 20/1 n-hexaneꢁCH2Cl2 give a
/
orange precipitate was formed. The
benzene were distilled from sodiumꢀ
/
benzophenone.
Acetonitrile, dichloromethane were distilled from cal-
cium hydride, and methanol from magnesium. All other
solvents and reagents were of reagent grade and were
used as received. Metal carbonyls, allyl bromide and
NH4S2P(OEt)2 were purchased from Strem, Merck and
Janssen, respectively. The compounds [Et4N][Cr(h2-
/
/
mixture of yellowꢁ
orange crystalline products [W(h3-
/
C3H5)(CO)2{h2-S2P(OEt)2}]2(m-dppe) (4) and 5.
S2CNC5H10)(CO)4]
[15]
and
[Et4N][W{h2-
3.3.2. Method B
S2P(OEt)2(CO)4] [8] were prepared according to the
literature methods. Elemental analyses and X-ray dif-
fraction studies were carried out at the Regional Center
of Analytical Instrument located at the National Taiwan
University.
Dppe (0.198 g, 0.5 mmol) was dissolved in CH2Cl2 (5
ml) and the solution was added slowly to a flask
containing a solution of 3 (0.523 g, 1.0 mmol) in
CH2Cl2 (10 ml) during a period of 5 min. The solution
was stirred for 10 min and the solvent was removed in
vacuo till about 5 ml. Methanol (15 ml) was added to
3.2. (Acetonitrile)(h3-allyl)(dicarbonyl)(h2-
diethyldithiophosphato)tungsten(II) (3)
the flask and the solution was stored at ꢃ
to give yellow precipitates. The precipitate was collected
by filtration (G4) washed with n-hexane (2ꢄ10 ml) and
/
18 8C for 12 h
/
Ten milliliter of CH2Cl2 was added to a 100 ml flask
containing [W(CH3CN)2(h3-C3H5)(CO)2(Br)] (0.442 g,
1.0 mmol) and [NH4][S2P(OEt)2] (0.203 g, 1.0 mmol) at
ambient temperature. After stirring for 10 min, the
solvent was removed in vacuo. The residue was
then dried in vacuo yielding 0.69 g (96%) of 4 Spectro-
scopic data of 4: IR (KBr) y (CO) 1937(vs), 1857(vs)
cmꢃ1
.
31P{1H}-NMR (202 MHz, CDCl3, 298 K): d 32.1
(dt, J(PP) 20.2 Hz, J(WP) 101.4 Hz), 108.5 (t, J(PP)
3
1
20.2 Hz, PS2). H-NMR (500 MHz, CDCl3, 298 K): d
abstracted by diethyl ether (2ꢄ
ml) was added to the solution and a yellowꢁ
precipitate was formed. The precipitate was collected by
filtration (G4) washed with cold n-hexane (2ꢄ10 ml)
/5 ml). n-Hexane (40
1.10 (t, 3J(HH) 9.7 Hz, 12H, OCH2CH3), 1.76 (d,
J(HH) 9.7 Hz, 4H, Hanti of allyl), 2.30, 2.81 (m, 4H,
PCH2), 3.48 (m, 2H, CH of allyl), 3.56 (m, 4H, Hsyn of
allyl), 3.72 (m, 8H, OCH2). 13C{1H}-NMR (125 MHz,
/orange
/
3
and then dried in vacuo yielding 0.42 g (82%) of 3.
Recrystallizations using a mixture of cold 20/1 n-
CDCl3, 298 K): d 15.8 (d, J(PC) 8.6 Hz, OCH2CH3),
26.3 (dd, J(PC) 11.6, 11.1 Hz, PCH2), 50.9 (br, CHꢁ
/
2
hexaneꢁ
/
diethyl ether give the yellowꢁ
/
orange crystalline
product [W(CH3CN)(h3-C3H5)(CO)2{h2-S2P(OEt)2}]
CH2), 62.0 (d, J(PC) 6.8 Hz, OCH2), 74.2 (s, CH2ꢁ
/
2
CH), 214.6 (d, J(PC) 7.7 Hz, CO). MS (FAB, NBA):
Yih, Kuang-Hway
