Conversion of η2-phosphinocarbene complexes into tungstaphosphabicyclo[1.1.0]butanone units

Article abstract of DOI:10.1016/S0022-328X(97)00632-3

Cationic η²-phosphinocarbene complexes [η²-C₅H₅(CO)(PMe₃)[PF ₆] (R=Me, Ph, Tol) react at -78°C with alkyl isonitriles R′NC (R′=Me, ^tBu) to provide tungstaphosphabicyclo[1.1.0]butanone complexes [η⁵-C₅H₅(R′NC)(PMe ₃)[PF₆] in high yields. The constitution of the yellow bicyclic compounds was determined by spectroscopic investigations and, in the case of the 4-methylphenyl substituted compound 2c, additionally by X-ray single crystal structure analysis. Crystal data for 2c are as follows: space group P2₁/n (No. 14), a=907.80(10), b=3658.1(6), c=1085.2(2) pm, α=90°, β=106.27(1)°, γ=90°, Z=4.

Full text of DOI:10.1016/S0022-328X(97)00632-3

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.
Journal of Organometallic Chemistry 553 1998 103–109
Conversion of h2-phosphinocarbene complexes into
w
x
tungstaphosphabicyclo 1.1.0 butanone units
a
b
b
a,)
Th. Lehotkay , K. Wurst , P. Jaitner , F.R. Kreißl
a
Anorganisch-chemisches Institut der Technischen UniÕersitat Munchen, Lichtenbergstraße 4, D-85747 Garching, Germany
¨
¨
b
Institut fur Anorganische, Allgemeine und Theoretische Chemie der UniÕersitat Innsbruck, Innrain 52a, A-6020 Innsbruck, Austria
¨
¨
Received 12 April 1997
Abstract
2
2
w
Ž
.Ž
.
w
x Ž
.
Cationic h -phosphinocarbene complexes h -C5H5 CO PMe3
PF6 RsMe, Ph, Tol react at y788C with alkyl
isonitriles RX N C
C5H5 R NC PMe3
R s M e,
B u
w
h -
X
t
5
Ž
.
w x
to provide tungstaphosphabicyclo 1.1.0 butanone com plexes
PF6 in high yields. The constitution of the yellow bicyclic compounds was determined by
w
X
Ž
.Ž
.
x
spectroscopic investigations and, in the case of the 4-methylphenyl substituted compound 2c, additionally by X-ray single crystal structure
Ž . Ž .
Ž
.
Ž .
analysis. Crystal data for 2c are as follows: space group P21rn No. 14 , as907.80 10 , bs3658.1 6 , cs1085.2 2 pm, as908,
Ž .
bs106.27 1 8, gs908, Zs4. q 1998 Elsevier Science S.A.
2
w
x
Keywords: h -Phosphinocarbene complex; Tungstaphosphabicyclo 1.1.0 butanone complex; Metalla–phospha–carbon ring system
1. Introduction
The structural and chemical properties of transition metal complexes with three-membered metalla–phospha–carbon
ring systems have been studied for more than twenty years. Next to the large group of phosphinomethanide complexes
2
w
x
with different metal-ligand parameters L M 1–4 , few examples of h -phosphinocarbene complexes have been
w
xn
synthesized and characterized so far 5–9 .
2
5
w
Ž
.Ž
.
Ž
X R,
The reactivity of the h -phosphinocarbene complexes of tungsten h -C5H5 CO PMe3
X
w
x w
x.
R salkyl, aryl; Xs BF4 , PF6 is comparable to well-known acyclic carbene complexes of tungsten in lower
oxidation state 10–13 . In the presence of electrophiles like MeSq dicationic tungstaphosphathiabi-
w
x
w
x
w x
cyclo 1.1.0 butane complexes A are formed 14 . On the other hand, selected nucleophiles like trialkyl phosphines or
the cyclopentadienyl anion C5H5 add at the carbene carbon atom providing phosphoranylidene complexes B 15 or
-
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x
w
x
tungstaphosphacyclopropane complexes C 16 , respectively.
)
Corresponding author.
0022-328Xr98r$19.00 q 1998 Elsevier Science S.A. All rights reserved.

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Th. Lehotkay et al.rJournal of Organometallic Chemistry 553 1998 103–109
In contrast, simple substitution reactions of the adjacent carbonyl or phosphine ligands have not been reported so
5
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.Ž
.
far. For the structurally related neutral tantalum complexes h -C5H5 PMe3 H2
Me2 , different
w
x
addition and substitution reactions are known. With olefins or substituted isocyanides 17 , insertion into the Ta–H
bond takes place without any modification of the M–P–C ring system. Thus, with neohexene dimerization as well as
w
x
oligomerization is observed 18,19 .
2. Results and discussion
We now report the conversion of h2-phosphinocarbene complexes of tungsten with selected isonitriles into cationic
t
w
x
tungstaphosphabicyclo 1.1.0 butanone complexes. The addition of both MeNC and more bulky isonitriles like BuNC
5
w
Ž
.Ž
.
w
x Ž .
to h -C5H5 CO PMe3
PF6 RsMe, Ph, Tol generates at y788C the cationic species 2a–3c in
excellent yields.
The deep yellow, diamagnetic compounds are insoluble in nonpolar solvents like diethylether or pentane but
slightly soluble in dichloromethane. The constitution and structure of 2a–3c are confirmed by elemental analysis,
1
infrared, H, 13C, and 31 P NMR spectroscopy and, in the case of 2c, additionally by an X-ray single crystal structure
analysis.
The infrared spectra of 2a–3c in dichloromethane exhibit in the region of 2126 to 2167 cmy1 characteristic
absorptions for the nCN stretching vibrations of the isocyanide ligand and in the range of 1639 to 1659 cmy1 the nCO
stretching frequencies for the bridging carbonyl group.
In the phosphorus NMR spectra the significant strong shielding of the endocyclic phosphorus nucleus together with
1
31
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.
W– P of about 195 Hz indicate the retention of the
the relatively small metal–phosphorus coupling constant J
w
x
tungsten–phosphorus–carbon ring system 20–23 .

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Th. Lehotkay et al.rJournal of Organometallic Chemistry 553 1998 103–109
105
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Fig. 1. ORTEP plot of 2c 50% probability .
The 13C NMR spectra also agree with the proposed structure of 2a–3c. Of special interest are the data of both ring
carbon atoms. Thus, the extreme shielding of the bridgehead carbon within ds3 to 7 ppm and the downfield shift of
w
x
w x
the ring carbonyl carbon atom are good indications for the tungstaphosphabicyclo 1.1.0 butanone ring structure 24 .
Both signals split into a doublet of doublets due to spin–spin interactions with the endo- and the exocyclic phosphorus
atoms.
Ž
.
The X-ray single crystal structure determination reveals further details on the structural properties of 2c Fig. 1 .
The cation shows a tungsten–phosphorus–carbon ring that is fused to a second tungsten–carbon–carbon ring,
w
x
affording a tungstaphosphabicyclo 1.1.0 butanone system. The distances from tungsten to the cyclopentadienyl, the
trimethylphosphine, and to the isonitrile ligands are comparable to those found for other tungsten complexes. Within
Ž . Ž .
w
Ž .
are similar to those reported for cationic h -phosphinocarbene complexes 20 and other metalla–phospha–hetero-
Ž . Ž .
x
Ž . Ž .
w
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.
x
the tungsten–phosphorus–carbon ring the W 1 –P 1 238.3 3 pm and the P 1 –C 1 175.9 13 pm bond distances
2
w
x
w
x
w
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.
x
cyclic systems 24 . The W 1 –C 1 distance 236.6 13 pm is significantly elongated and is to be regarded as a W–C
w
x
single bond 24,25 . The PPh2-group is obviously bent away from the cyclopentadienyl ligand indicating sterical
hindrance to the bulky phenyl rings. Within the second fused three-membered ring the significantly shortened
Ž . Ž .
Ž
.
W 1 –C 2 bond distance lies within 211.2 13 pm still in the range of a tungsten carbene unit. The ligand sphere
around the tungsten atom could be described as a distorted octahedral polyeder with the cyclopentadienyl, the PPh2-
and the CO-fragments in a facial arrangement. Besides the description as a bicyclic system D the canonical form of an
3
Ž . Ž . Ž .
Ž
.
h -allylic arrangement E can also be taken into account due to the fact that the four atoms P 1 , C 1 , C 2 and C 10
are coplanar.
Ž . Ž .
The linear conformation of the C-coordinated isonitrile ligand with slightly shortened W 1 –C 3 distance
210.2 14 pm , as well as the N 1 –C 3 113.9 14 pm triple- and N 1 –C 4 single-bond character 142 2 pm
reflect only little back donation from the metal to the isocyanide ligand.
w
Ž
.
x
Ž . Ž . Ž . Ž . Ž .
w
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.
x
w
x

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Th. Lehotkay et al.rJournal of Organometallic Chemistry 553 1998 103–109
2.1. Chemical properties
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x
In comparison to isostructural trimethylphosphine-substituted tungstaphosphabicyclo 1.1.0 butanone compounds
5
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.Ž
.
w
x
Ž
. w x
h -C5H5 CO PMe3
BF4 Rsalkyl, aryl 24 the isonitrile substituted representatives 2a–3c
are thermally more stable. Carbonyl extrusion is restricted even at room temperature. On refluxing a solution of 2c in
tetrahydrofurane the trimethylphosphine-substituted h2-phosphinocarbene complex 1c as well as the isonitrile-sub-
stituted h2-phosphinocarbene complex 4c are formed in a temperature-dependent ratio. As both cationic species show
comparable solubility in most common solvents, a separation has not been successful.
3. Experimental details
Standard inert-atmosphere techniques were used for the manipulation of all reagents and reaction products. All
˚
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.
solvents were dried according to conventional methods and stored under nitrogen over molecular sieves 4 A .
1
Infrared spectra were recorded on a Perkin-Elmer FT-IR 1600 spectrometer. H, 13C, and 31 P NMR spectra were
taken in CDCl3, CD3CN, and CD2Cl2 on a Jeol JNM-GX 270 1H, 270.27; 13C, 67.94; P, 109.37 MHz
31
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.
Ž13
.
spectrometer. Chemical shifts are quoted as d in ppm with respect to the deuterated solvents C and its residual
proton resonances H , and to aqueous 85% H3PO4 for 31 P NMR, respectively. Mass spectra were recorded on a
Ž1
.
184
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.
Finnigan MAT 90 spectrometer molecular mass relative to
isonitriles MeNC and BuNC were prepared as described in the literature 26 .
W . The starting materials 1a–1c as well as the
t
w
x
5
[
(
)(
)
[
] ( )
BF4 2a
3.1. Synthesis of h -C5 H5 MeNC PMe3
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.
To a solution of 0.41 g 0.63 mmol of 1a in 20 ml dichloromethane were added the stoichiometric amounts of 0.03
g of methylisonitrile at y788C. The solution immediately turned to bright yellow and was stirred for 1 h at y788C.
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.
Recrystallization from CH2Cl2rEt2Orpentane afforded a bright microcrystalline powder. Yield 0.39 g 89% of 2a.
Element. Anal. Found: C, 42.72; H, 4.37; N, 1.91; W, 26.90. C25 H30 BF4 NOP2W, calcd.: C, 43.28; H, 4.36; N, 2.02;
1
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.
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.
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.
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.
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W, 26.54%. H NMR CDCl3 : 7.56–6.83 m, 10H, C6 H5 ; 4.61 s, 5H, C5 H5 ; 3.15 s, 3H, C H3NC ; 1.41 d, 3H,
3
2
2
13
2
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.
.
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.
.
Ä1
4
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.
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.
J PH s8.6, C–C H3 ; 1.20 d, 9H, J PH s8.4, PMe3 . C H NMR CD3CN : 249.1 dd, J PC s9.2,
1
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.
.
.
Ž
.
.
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.
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.
.
Ž
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.
.
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J PC s9.2, W–CO ; 135.5–125.9 C6 H5 ; 90.9 CH3NC ; 87.9 C5H5 ; 31.6 t, J CN s3.7, CH3NC ; 18.1
1
1
31
2
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.
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.
.
Ä1
31
4
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.
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.
.
PMe3, J PC s33.1 ; 10.9 C–CH3 ; 3.9 d, J PC s24.8, W–C . P H NMR CD2Cl2 : y25.1 d, J PP s
1
2
1
Ž183
.
.
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Ž
Ž183
.
.
Ž
w
31
2.9, J
W– P s251.0, PMe3 ; y35.4 d, J PP s4.3, J
W– P s198.2 PPh2 . IR CH2Cl2 : nCN 2165
vs; nCO 1659 s, 1606 w cmy1. MS FAB : 606 K , 578 KyCO , 565 KyCH3NC , 537 KyCO–CH3NC .
Ž
.
w xq
w
xq
w
xq
xq
5
[
(
)(
)
[
] (
BF4 2b
)
3.2. Synthesis of h -C5 H5 MeNC PMe3
Ž
.
Ž
.
According to Section 3.1, 0.39 g 0.55 mmol of 1b and 0.03 g of methylisonitrile yielded 0.37 g 90% of 2b.
Element Anal. Found: C, 46.87; H, 4.22; N, 1.77. C30 H32 BF4 NOP2W, calcd.: C, 47.67; H, 4.27; N, 1.85; W, 24.36%.
1
2
4
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.
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.
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.
.
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.
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H NMR CDCl3 : 7.57–7.10 m, 15H, C6 H5 ; 5.08 t, 5H, J NH s3.4, C5 H5 ; 3.69 s, 3H, C H3NC ; 1.20 d, 9H,
13
2
2
Ž
.
.
Ä1
4
Ž
.
Ž
Ž
.
Ž
.
.
J PH s9.3, PMe3 . C H NMR CD3CN : 246.1 dd, J PC s9.2, J PC s7.4, W–CO ; 133.5–116.7
1
1
Ž
.
.
.
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.
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.
Ž
.
Ž
Ž
.
.
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.
C6 H5 ; 94.0 C5H5 ; 90.0 CH3NC ; 32.1 CH3NC ; 17.0 PMe3, J PC s33.0 ; 6.2 dd, J PC s24.8,
2
31
2
1
31
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.
Ä1
4
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.
Ž
Ž
.
Ž183
.
.
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J PC s7.4, W–C . P H NMR CD2Cl2 : y27.1 d, J PP s4.3, J
W– P s248.0, PMe3 ; y40.2 d,
2
1
Ž183
.
.
Ž
.
Ž
.
w xq
31
J PP s4.3, J
W– P s191.1 PPh . IR CH2Cl2 : nCN 2167 vs; nCO 1652 s cmy1. MS FAB : 668 K ,
w
xq
w
xq
2w
xq
w
xq
640 KyCO , 627 KyCH3NC , 599 KyCO–CH3NC , 564 KyPMe3–CH3NC .

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Th. Lehotkay et al.rJournal of Organometallic Chemistry 553 1998 103–109
107
5
[
(
)(
)
[ ] ( )
BF4 2c
3.3. Synthesis of h -C5 H5 MeNC PMe3
Ž
.
The procedure employed was analogous to that in Section 3.1. using 0.46 g 0.63 mmol of 1c and 0.03 g of
methylisonitrile. Recrystallization from CH2Cl2rEt2Orpentane afforded a bright yellow microcrystalline powder.
Ž
.
Yield 0.44 g 91% of 2c. Element anal. found: C, 47.66; H, 4.43; N, 1.83; W, 23.69. C31H34 BF4 NOP2W. calcd.: C,
1
4
Ž
.
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.
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.
48.36; H, 4.45; N, 1.82; W, 23.92%. H NMR CDCl3 : 7.82–6.94 m, 14H, C6 H4r5 ; 5.06 t, 5H, J NH s3.4,
2
2
13
.
Ž
Ž
.
.
Ž
.
Ž
Ž
.
.
.
Ä1
4
C5 H5 ; 3.67 t, 3H, J NH s3.9, C H3NC ; 2.26 s, 3H, Tol–C H3 ; 1.20 d, 9H, J PH s9.3, PMe3 . C H
Ž
.
Ž
.
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.
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.
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.
NMR CD3CN : 246.3 W–CO ; 137.6–129.1 C6 H5r4 ; 94.1 C5H5 ; 89.9 CH3NC ; 31.7 CH3NC ; 21.2
1
31
2
1
31
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.
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.
.
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4
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.
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.
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.
Tol–CH3 ; 17.0 PMe3, J PC s33.1 . P H NMR CD2Cl2 : y27.0 d, J PP s4.3, J
W– P s249.6,
W– P s192.5, PPh2 . IR CH2Cl2 : nCN 2165 vs; nCO 1639 s, 1697 w
xq xq xq xq
2
1
31
.
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.
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.
Ž183
.
.
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.
PMe3 ; y41.4 d, J PP s4.3, J
cmy1. MS FAB : 682 K , 654 KyCO , 641 KyCH3NC , 613 KyCO–CH3NC , 578 KyCO–PMe3
.
Ž
w xq
w
w
w
w
5
t
[
(
)(
)
[
] ( )
BF4 3a
3.4. Synthesis of h -C5 H5 BuNC PMe3
Ž
.
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.
According to Section 3.1, 0.38 g 0.58 mmol of 1a and 0.05 g of tert-butylisonitrile yielded 0.35 g 82% of 3a.
Element anal. found: C, 44.88; H, 4.73; N, 1.5; W, 22.04. C28 H36 BF4 NOP2W. calcd.: C, 45.70; H, 4.94; N, 1.90; W,
1
4
3
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.
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.
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.
.
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.
25.02%. H NMR CDCl3 : 7.96–7.19 m, 10H, C6 H5 ; 5.02 t, 5H, J NH s3.9, C5 H5 ; 1.80 d, 3H, J PH s7.8,
2
t
13
2
.
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.
.
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.
Ä1
4
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.
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.
C–C H3 ; 1.61 d, 9H, J PH s9.3, PMe3 ; 1.24 s, 9H, BuNC ;. C H NMR CD3CN : 247.8 dd, J PC s11.0,
2
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.
.
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.
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.
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.
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.
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.
.
J PC s10.1, W–CO ; 135.4–129.0 C6 H5 ; 88.7 Me3CNC ; 87.9 C5H5 ; 59.9 Me33C1 NC ; 30.2 Me3CNC ;
1
1
2
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.
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.
Ä1
4
31
Ž
18.0 PMe3, J PC s33.1 ; 10.6 C–CH3 ; 3.5 dd, J PC s24.8, J PC s6.4, W–C . P H NMR CD2Cl2 :
2
1
2
1
31
Ž
Ž
.
Ž183
.
Ž
Ž
.
Ž183
. .
W– P s195.4 PPh2 .
t
y19.4 d, J PP s4.3, J
W– P s245.3, PMe3 ; y29.5 d, J PP s2.9, J
IR CH2Cl2 : nCN 2127 vs; nCO 1659 s cmy1. MS FAB : 648 K , 620 KyCO , 565 Ky BuNC , 537
Ž
.
Ž
.
w xq
w
xq
w
xq
t
w
xq
KyCO– BuNC .
5
t
[
(
)(
)
[ ] ( )
BF4 3c
3.5. Synthesis of h -C5 H5 BuNC PMe3
Ž
.
This compound was prepared analogously to 2a using 0.45 g 0.62 mmol of 1c and 0.06 g of tert-butylisonitrile.
Ž
.
Recrystallization from CH2Cl2rEt2Orpentane afforded a bright microcrystalline powder. Yield 0.40 g 80% of 3c.
Element anal. found: C, 49.01; H, 4.99; N, 1.37; W, 20.52. C34 H40 BF4 NOP2W, calcd.: C, 50.30; H, 4.97; N, 1.73; W,
1
Ž
.
Ž
Ž
.
Ž
.
Ž
.
Ž
22.68%. H NMR CDCl3 : 7.82–6.92 m, 14H, C6 H4r5 ; 5.28 s, 5H, C5 H5 ; 2.27 s, 3H Tol–C H3 ; 1.40 s, 9H,
t
2
13
2
2
.
.
Ž
.
.
Ä1
4
Ž
.
.
Ž
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.
Ž
.
BuNC ; 1.23 d, 9H, J PH s9.8, PMe3 . C H NMR CD3CN ; 245.4 dd, J PC s11.0, J PC s11.0,
Ž
.
Ž
.
Ž
Ž
.
Ž
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.
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.
W–CO ; 137.4–127.1 C6 H4r5 ; 93.2 Me3CNC ; 88.5 C5H5 ; 60.3 Me3CNC ; 30.3 Me3CNC ; 21.2 Tol–CH3 ;
1
1
31
2
Ž
Ž
.
.
Ž
Ž
.
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.
Ä1
4
.
Ž
Ž
.
17.0 PMe3, J PC s32.2 ; 5.6 d, J PC s22.4, W–C . P H NMR CD2Cl2 : y26.5 d, J PP s4.3,
1
2
1
Ž183
.
.
Ž
.
Ž183
. . Ž .
W– P s191.1 PPh2 . IR CH2Cl2 : nCN 2126 vs;
31
31
J
W– P s241.0, PMe3 ; y40.3 d, J PP s4.3, J
nCO 1640 s cmy1. MS FAB : 696 K , 613 Ky BuNC .
t
Ž
.
w xq
w
xq
5
[
(
)(
)
[ ] ( )
BF4 2c
3.6. Thermal treatment of h -C5 H5 MeNC PMe3
Ž
.
A suspension of 0.32 g 0.42 mmol of 2c in 5 ml of tetrahydrofurane was refluxed for 1 h. After several minutes
the suspension turned to an orange-brown solution. The formation of both h2-phosphinocarbene complexes 1c and 4c
could be observed by infrared spectroscopy.
1
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.
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.
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.
Ž
.
Ž
2
1c: H NMR CDCl3 : 7.57–6.97 m, C6 H4r5 ; 5.83 s, 5H, C5 H5 ; 2.29 s, 3H Tol–C H3 ; 1.30 d, 9H,
2
31
2
1
31
Ž
.
.
Ä1
4
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.
Ž
.
Ž183
.
.
Ž
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.
J PH s9.9, PMe3 . P H NMR CDCl3 : y24.2 d, J PH s6.7, J
W– P s385.2 ; y111.3 d, J PP
s6.7, PPh2 . IR CH2Cl2 : nCO 1979 s, 1930 vs cmy1. MS FAB : 641 K , 613 KyCO .
.
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.
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.
w xq
w
xq
1
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.
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.
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.
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.
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1
.
4c: H NMR CDCl3 : 7.57–6.97 m, C6 H4r5 ; 5.30 s, 5H, C5 H5 ; 3.68 s, 3H, MeNC ; 2.29 s, 3H Tol–C H3 ;
31
2
2
31
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.
Ä1
4
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.
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.
.
.
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Ž183
.
W– P s
1.22 m, 9H, PMe3 . P H NMR CDCl3 : y28.3 d, J PP s10.7 ; y116.4 d, J PP s10.7, J
131.4 PPh2 . IR CH2Cl2 : nCN 2155 vs cmy1. MS FAB : 654 K , 613 KyMeNC .
.
Ž
.
w xq
w
xq
4. X-ray structure determination of 2c
Suitable crystals of 2c were grown from dichloromethanerdiethyl ether at y308C. Crystal data together with
details of the data collection and structure refinement are listed in Table 1. A platelet of dimension 0.3=0.3=0.04
mm was measured on a Siemens P4 diffractometer with graphite-monochromatized Mo K a-radiation. The unit cell
parameters were determined and refined from 32 randomly selected reflections in the 2Q range of 10.5 to 22.08,

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108
Th. Lehotkay et al.rJournal of Organometallic Chemistry 553 1998 103–109
Table 1
Crystal data and structure refinement for 2c
Molecular formula
C31H34 BF4 NOP2WPCH2Cl2
854.12
y1
Ž
.
Formula weight g mol
Ž .
Ž .
Temperature K
213 2
Ž
.
Radiation
Mo K a 71.073 pm
Crystal system
Space group
Monoclinic
Ž
.
P21 rn No. 14
Unit cell dimensions
Ž
.
Ž .
a pm
Ž
907.80 10
Ž .
3658.1 6
.
b pm
Ž
.
Ž .
c pm
1085.2 2
Ž
.
Ž .
b deg
106.27 1
3
Ž
.
Ž .
Volume nm
3.4594 9
Z
4
y3
Ž
.
rcalcd g cm
absorption coefficient mm
1.640
3.634
1688
0.3=0.3=0.04
10.5 to 22.0
y1
Ž
.
Ž
.
F 000
Crystal dimension mm
3
Ž
.
Ž
.
u range for data collection deg
Index ranges
Reflections collected
Independent reflections
0FhF9, 0FkF37, y10FlF9
4267
Ž
.
3972 Rint s0.0418
Ž .
Reflections with I)2s I
2797
Absorption correction
Refinement method
C-scan
Full-matrix least-squares on F2
3971r0r399
Datarrestraintsrparameters
Goodness-of-fit on F2
1.057
w
Ž .x
Final R indices I)2s I
R1s0.0476, wR2 s0.0977
R1s0.0868, wR2 s0.1173
931 and y965
Ž
.
R indices all data
Largest different peak and hole e nm
y3
Ž
.
obtained by P4 automatic routines. Diffraction intensities were collected up to 2Q-438 via v-scans and corrected for
w
x
Lorentz and polarisation effects. An empirical absorption correction 27 based on a series of c-scans was applied to
Ž
.
Ž
.
the data max. and min. transmission: 1.000 and 0.611 . The structure was solved by direct methods SHELXS-86
2
2
w
x
Ž
.
w
x
w Ž
28 and refined by full matrix least-squares against F SHELXL-93 29 . The function minimized was Ý w Fo y
F2
with the weight defined as w s s2 Fo q xP qyP with Ps Fo q2F r3 xs0.047 and ys20.143 .
2
1
2
2
2
2
c
.
x
w
Ž
.
Ž
.
x
Ž
.
Ž
.
c
All nonhydrogen atoms were refined with anisotropic displacement parameters. Hydrogen atoms were included in
Table 2
Ž
.
Ž
.
Selected bond lengths pm and angles deg for 2c
Ž . Ž . Ž .
W 1 –P 2 248.9 3
Ž . Ž . Ž .
W 1 –C 2 –C 1
Ž .
80.1 8
W 1 –P 1 238.3 3
Ž . Ž .
Ž .
Ž . Ž . Ž .
W 1 –C 3 –N 1
Ž .
176.3 11
Ž . Ž .
W 1 –C 2
Ž
.
.
.
.
.
.
.
.
Ž . Ž . Ž .
Ž .
132.48 12
W 1 –C 1
Ž . Ž .
236.6 13
P 1 –W 1 –P 2
Ž
Ž . Ž . Ž .
Ž .
211.2 13
P 1 –W 1 –C 1
43.5 3
Ž .
68.8 3
Ž . Ž .
Ž
Ž . Ž . Ž .
W 1 –C 3
210.2 14
P 1 –W 1 –C 2
Ž . Ž . Ž .
P 1 –W 1 –C 3
Ž . Ž .
P 1 –C 17
Ž
Ž .
86.3 3
P 1 –C 1
175.9 13
Ž .
Ž
.
.
Ž
Ž . Ž . Ž .
P 1 –C 1 –C 2
P 1 –C 1 –C 10
Ž .
103.1 8
181.1 12
Ž .
O 1 –C 2
Ž
Ž
Ž . Ž .
Ž
.
Ž .
P 1 –C 23
Ž . Ž .
183.3 13
132.6 9
Ž
Ž .
Ž . Ž .
Ž .
119.3 14
P 2 –W 1 –C 1
Ž . Ž . Ž .
90.6 3
Ž . Ž .
Ž
Ž .
N 1 –C 3
113.9 14
P 2 –W 1 –C 2
81.1 3
Ž .
80.5 3
Ž . Ž .
Ž .
Ž . Ž . Ž .
N 1 –C 4
142 2
P 2 –W 1 –C 3
Ž .
Ž
.
Ž .
Ž . Ž . Ž .
Ž
.
C 1 –C 10
148 2
Ž .
O 1 –C 2 –C 1
Ž . Ž . Ž .
135.9 12
Ž . Ž .
Ž .
C 1 –C 2
149 2
C 1 –W 1 –C 3
89.1 4
Ž .
Ž . Ž . Ž .
Ž .
Ž . Ž . Ž .
W 1 –P 1 –C 1
67.8 4
C 1 –W 1 –C 2
38.4 4
Ž . Ž .
Ž
.
.
Ž .
Ž . Ž .
Ž
.
.
.
Ž .
W 1 –P 1 –C 17
126.5 5
C 1 –P 1 –C 17
113.8 6
Ž .
113.3 6
Ž . Ž .
Ž
Ž .
Ž . Ž .
Ž
W 1 –P 1 –C 23
123.5 4
Ž .
C 1 –P 1 –C 23
Ž . Ž . Ž .
Ž . Ž .
Ž
Ž
.
.
W 1 –C 1 –P 1
68.8 4
C 2 –C 1 –C 10
123.2 11
Ž .
123.5 5
Ž . Ž . Ž .
Ž .
Ž . Ž . Ž .
W 1 –C 1 –C 2
61.5 6
C 3 –W 1 –C 2
Ž . Ž .
Ž
.
Ž .
Ž . Ž . Ž .
Ž
W 1 –C 1 –C 10
140.2 9
Ž .
C 3 –N 1 –C 4
Ž . Ž .
C 17 –P 1 –C 23
174.7 13
Ž . Ž . Ž .
W 1 –C 2 –O 1
Ž
.
Ž .
143.2 9
105.3 6

(
)
Th. Lehotkay et al.rJournal of Organometallic Chemistry 553 1998 103–109
109
idealized positions and were refined with isotropic displacement parameters 1.2 and 1.5 times higher than U of the
eq
attached carbon atoms. Selected bond lengths and angles for 2c are shown in Table 2.
Acknowledgements
We would like to thank Mrs. Dumitrescu for recording the mass spectra, Mr. Barth for the elemental analysis, and
the Fonds der Chemischen Industrie and the Deutschen Forschungsgemeinschaft for the support of this work.
Supporting Information Available: Tables of crystallographic and structure refinement data, atomic coordinates and
isotropic displacement parameters, bond lengths and angels, anisotropic displacement parameters, and hydrogen
Ž
.
coordinates 11 pages . Ordering information is given on any current masthead page. Further details of the crystal
structure investigation are available on request from the Fachinformationszentrum Karlsruhe, Gesellschaft fur
¨
wissenschaftlich-technische Information mbH, D-76344 Eggenstein-Leopoldshafen 2, Germany, on quoting the
depository number CSD-407342, the names of the authors, and the journal citation.
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¨