Tungstaarsirenes
Organometallics, Vol. 16, No. 9, 1997 1877
Ta ble 2. Selected Bon d Dista n ces a n d An gles for 2c
Bond Distances (pm)
As(1)-C(3)
192.3(5)
193.8(6)
192.1(6)
249.7(6)
197.8(6)
W(1)-C(1)
W(1)-C(2)
O(1)-C(1)
O(2)-C(2)
C(3)-C(41)
201.8(6)
202.0(6)
112.2(7)
112.7(7)
146.4(8)
As(1)-C(21)
As(1)-C(31)
W(1)-As(1)
W(1)-C(3)
Bond Angles (deg)
As(1)-W(1)-C(3)
As(1)-C(3)-W(1)
W(1)-As(1)-C(21)
W(1)-As(1)-C(31)
W(1)-As(1)-C(3)
49.28(16)
79.9(2)
125.97(17)
126.76(17)
50.87(17)
C(1)-W(1)-C(2)
C(21)-As(1)-C(31)
C(3)-As(1)-C(21)
C(3)-As(1)-C(31)
88.6(2)
107.2(2)
106.2(2)
116.4(2)
Torsion Angles
C(1)-W(1)-C(3)-As(1)
C(1)-W(1)-C(3)-C(41)
W(1)-C(3)-As(1)-C(21)
175.1(2)
-7.9(9)
123.5(2)
C(2)-W(1)-C(3)-As(1)
C(2)-W(1)-C(3)-C(41)
W(1)-C(3)-As(1)-C(31)
87.5(2)
-95.4(9)
-117.2(2)
1H NMR (CD2Cl2, 270 MHz): δ 7.54-7.31 (m, 10H, C6H5), 6.12
(s, 5H, C5H5), 2.84 (s, 3H, CH3) 13C NMR (CDCl3, 68 MHz): δ
266.4 (s, J (183W-13C) ) 66.2 Hz, WdC), 202.9 (s, J (183W-13C)
) 171.9 Hz, WsCO), 134.7-127.3 (m, C6H5), 94.4 (s, C5H5),
34.2 (s, CH3).
Sch em e 3
P r ep a r a tion of [(η 5-C5H5)(CO)2WdC(P h )sAsP h 2]][P F 6]
(2b). This compound was prepared analogously to 2a , using
0.41 g (1.04 mmol) of 1b in 20 mL of diethyl ether by addition
of equimolar amounts of thallium hexafluorophosphate (0.36
g) and chlorodiphenylarsine (0.19 mL). A yellow solid was
isolated: yield 0.71 g (89%). Anal. Calcd for C26H20AsF6O2-
PW: C, 40.65; H, 2.62; W, 23.93. Found: C, 39.82; H, 2.69
W, 24.11. IR (CH2Cl2): νCO 2065 vs, 2007 vs cm-1
. MS
(FAB): m/e 623 [M]+, 595 [M - CO]+. 1H NMR (CD2Cl2, 270
MHz): δ 7.66-7.14 (m, 15H, C6H5), 6.17 (s, 5H, C5H5). 13C
NMR (CD2Cl2, 68 MHz): δ 258.4 (s, WdC), 203.6 (s, WsCO),
134.7-126.9 (m, C6H5), 94.3 (s, C5H5).
logues, differences are evident in the less pronounced
thermal stability as well as in the reaction behavior
toward trimethylphosphine. Thus, in the case of 2c
cleavage of the AsPh2 unit is observed (A), providing
the original carbyne complex 1c. In contrast, the η2-
P r ep a r a tion of [(η5-C5H5)(CO)2WdC(Tol)sAsP h 2][P F 6]
(2c). By the method used for 2a , 0.41 g (1.00 mmol) of 1c,
0.35 g of thallium hexafluorophosphate, and 0.18 mL of
chlorodiphenylarsine yielded 0.70 g (90%) of a yellow product.
Anal. Calcd for C27H22AsF6O2PW: C, 41.46; H, 2.83; W, 23.50.
Found: C, 41.30; H, 2.77; W, 23.67. IR (CH2Cl2): νCO 2060
vs, 2002 vs cm-1. MS (FAB): m/e 637 [M]+, 609 [M - CO]+.
1H NMR (CDCl3, 270 MHz): δ 7.60-7.12 (m, 14H, C6H4/5), 6.12
(s, 5H, C5H5), 2.29 (s, 3H, CH3). 13C NMR (CDCl3, 68 MHz):
δ 257.8 (s, WdC), 204.4 (s, J (183W-13C) ) 167.3 Hz, WsCO),
145.4-127.7 (m, C6H4/5), 94.1 (s, C5H5), 21.7 (s, CH3).
X-Ra y Sin gle Cr ysta l Str u ctu r e Deter m in a tion of 2c.
Suitable crystals were grown from dichloromethane/diethyl
ether at -30 °C. Crystal data together with details of the data
collection and structure refinement are listed in Table 1.
Preliminary examination and data collection were carried out
on an imaging plate diffraction system (IPDS; Stoe & Cie)
equipped with a rotating anode (ENRAF-Nonius FR591; 50
kV; 80 mA; 4.0 kW) and graphite monochromated Mo KR
radiation. The data collection was performed at 173 ( 1 K
within the θ range 2.19° < θ < 24.56° with an exposure time
of 3 min/image (oscillating scan modus from æ ) 0.0° to 360°
with ∆æ ) 1°20). A total of 32 066 reflections were collected,
from which 8926 independent reflections remained and were
used for all calculations. Data were corrected for Lorentz and
polarization effects, intensity decay, and/or absorption effects.21
The unit cell parameters were obtained by least-squares
refinements of 1999 reflections with the program Cell.21 The
structure was solved by direct methods and refined with
standard difference Fourier techniques. All “heavy atoms” of
the asymmetric unit were anisotropically refined. All hydro-
gen atoms were calculated in ideal positions (riding model).
phosphinocarbene complex [(η2-C5H5)(CO)2WdC(Tol)sAs-
Ph2][PF6] leads to a tungstaphosphaoxacyclopentene
complex19 (B).
Exp er im en ta l Section
Standard inert-atmosphere techniques were used for the
manipulation of all reagents and reaction products. Infrared
spectra were recorded on a Perkin-Elmer FT-IR 1600 spec-
trometer. 1H, 13C, and 31P NMR spectra were taken in CDCl3
and CD2Cl2 on a J EOL J NM-GX 270 (1H, 270.27 MHz; 13C,
67.94 MHz; 31P, 109.37 MHz) spectrometer. The spectral
standard for 31P NMR was 85% H3PO4. Mass spectra were
recorded on a Finnigan MAT 90 spectrometer with FAB
techniques (nitrobenzyl alcohol (NBA) matrix, molecular mass
relative to 184W). The starting materials 1a -c as well as Ph2-
AsCl were prepared according to the literature. Tl[PF6] was
a commercial product from Strem Chemicals.
P r ep a r a tion of [(η 5-C5H5)(CO)2WdC(Me)sAsP h 2]][P F 6]
(2a ). To a solution of 0.36 g (1.08 mmol) of 1a in 20 mL of
diethyl ether was added successively stoichiometric amounts
of thallium hexafluorophosphate (0.38 g) and chlorodiphenyl-
arsine (0.19 mL) at -20 °C. The suspension was warmed to
room temperature and stirred for 18 h. Then the yellow solid
was isolated by filtration and washed several times with 10
mL of diethyl ether. The crude product was redissolved in
dichloromethane, and insoluble thallium chloride was removed
by filtration. Recrystallization from CH2Cl2/Et2O/pentane
provided a brownish yellow solid: yield 0.49 g (64%). Anal.
Calcd for C21H18AsF6O2PW: C, 35.72; H, 2.57; W, 26.04.
Found: C, 36.40; H, 2.84; W, 26.45. IR (CH2Cl2): νCO 2064
vs, 2007 vs cm-1. MS (FAB): m/e 561 [M]+, 533 [M - CO]+.
(20) Schu¨tt, W.; Herdtweck, E.; Hahn, F.; Kreissl, F. R. J . Orga-
nomet. Chem. 1993, 443, C33 and references cited therein.
(21) IPDS Operating System Version 2.7; Stoe
Darmstadt, Germany, 1996.
& Cie GmbH,