Polarity reversal in η2-phosphinocarbene and η2-arsinocarbene complexes of tungsten

Article abstract of DOI:10.1016/S0022-328X(99)00121-7

Trichloro- and trifluoroacetic acids CF₃COOH and CCl₃COOH react with cationic η²-phosphino-(Cp(CO)(PMe₃)W=C(R)-PPh ₂)(BF₄) as well as η²-arsinocarbene complexes of tungsten (Cp(C

Full text of DOI:10.1016/S0022-328X(99)00121-7

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 583 (1999) 120–125
Polarity reversal in h2-phosphinocarbene and h2-arsinocarbene
complexes of tungstenꢀ
Thomas Lehotkay a,*, Peter Jaitner b, Klaus Wurst b, Fritz R. Kreißl b
a Anorganisch-chemisches Institut der Technischen Uni6ersita¨t Mu¨nchen, Lichtenbergstrasse 4, D-85747 Garching, Germany
b Institut fu¨r Allgemeine, Anorganische und Theoretische Chemie der Uni6ersita¨t Innsbruck, Innrainstrasse 52, A-6020 Innsbruck, Austria
Received 30 June 1998; received in revised form 23 November 1998
Abstract
Trichloro- and trifluoroacetic acids CF3COOH and CCl3COOH react with cationic h2-phosphino-(Cp(CO)(PMe3)-
¸¹¹¹¹¹º
¸¹¹¹¹¹¹º
WꢀC(R)–PPh2)(BF4) as well as h2-arsinocarbene complexes of tungsten (Cp(CO)2 WꢀC(R)–AsPh2)(PF6) to form the correspond-
¸¹¹¹¹¹¹¹º
ing h2-phosphinomethanide (Cp(CO)(PMe3)(Y)W–C(H)(R)–PPh2)(BF4) (Y=CF3COO, CCl3COO) or h2-arsinomethanide com-
pounds (Cp(CO)2(CF3COO)¸W¹–¹C¹(H¹)¹(R¹)¹–¹AºsPh2)(PF6), respectively. Next to spectroscopic investigations, the constitution of the
new compounds is proved by X-ray single crystal structure determinations. © 1999 Elsevier Science S.A. All rights reserved.
Keywords: h2-Phosphinocarbene complexes; h2-Arsinocarbene complexes; h2-Phosphinomethanide complexes; h2-Arsinomethanide complexes
compounds e.g. h2-thiocarbene complexes (Cp(CO)-
1. Introduction
¸¹¹¹¹¹º
LMꢀC(R)–PPh2)(BF4) [9–11] (R=alkyl, aryl) and
trimethylphosphine substituted h2-phosphinocarbene
Transition metal complexes containing a metal car-
bon multiple bond can be classified as Fischer-type or
Schrock-type carbene or carbyne complexes with re-
spect to the metal ligand parameters and the chemical
properties of the metal carbon multiple bond [1–6].
Although most of these compounds can be related
to these two groups, some representatives show a
pronounced amphiphilicity for the metal carbon
multiple bond and therefore restrict a definite classi-
fication. Next to some acyclic carbene complexes like
Ropers’ (CO)2(PPh3)2RuꢀCF2 [7] or Caseys’ Cp-
complexes of molybdenum and tungsten (Cp-
¸¹¹¹¹¹º
(CO)LMꢀC(R)–PPh2)(BF4) [12,13] (R=alkyl, aryl) are
known.
Thus, in the presence of electrophiles like MeS+
dicationic tungsta-dithiabicyclo(1.1.0)butane [14] or
tungsta-thia-phosphabicyclo(1.1.0)butane
complexes
[15] (A) are formed, whereas nucleophiles like phosphi-
nes add to the metal carbon double bond affording
phosphoranylidene complexes [13] (B) (Scheme 1).
Further investigations have shown that other elec-
trophiles like H(BF4) or sulfur do not afford any addi-
tion products. These observations diminish the
amphiphilic character of the cyclic carbene complexes
[16] and underline the fact that the nucleophilicity of
the carbene carbon atom is not very significant, but
could be increased by a modification of the ligand
parameters.
(CO)2ReꢀCH(CH2)2C(CH3)3 [8] even
a few cyclic
ꢀ Dedicated to Professor Alberto Ceccon on the occasion of his
65th birthday.
* Corresponding author. Tel.: +49-89-289-13077; fax: +49-89-
289-13473.
E-mail address: kreissl@irz.tum.de (T. Lehotkay)
0022-328X/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(99)00121-7

T. Lehotkay et al. / Journal of Organometallic Chemistry 583 (1999) 120–125
121
Table 1
IR spectra of 3a–5c in dichloromethane
3a
3b
3c
4b
5c
wCO
2002 vs
2003 vs
1998 vs
2003 vs
2092 vs
2036 vs
wOCO 1716 vs
1717 vs
1760 vs
1717 vs
1701 vs
1696 vs
1718 s
1699w
1703 vs
cm−1 a characteristic absorption for the wCO-stretching
vibrations of the carbonyl ligands. In comparison to the
correspondent h2-phosphinocarbene complexes a sig-
nificant decrease of the M–CO back donation is recog-
nized due to electronic and sterical alterations at the
Scheme 1.
metal center. The stretching frequencies of the wOCO
-
group in the acetic anion appear as characteristic ester
double bands in the range of 1696–1760 cm−1. In the
1H-NMR spectra (Table 2) the addition of the trifluoro-
or trichloroacetic acids to the h2-carbene complexes is
reflected by a significant deshielding of all protons. The
chemical shift of the added proton in the range of
l=2.81–3.01 ppm is comparable to h2-thiomethanide
complexes described in the literature [17].
2. Results
Surprisingly, in the presence of trihalogenated acetic
acids like CF3COOH and CCl3COOH a (1,2)-addition
reaction on the metal carbon¸d¹o¹ub¹l¹e ¹bºond in cationic
h2-phosphino-(Cp(CO)(PMe3)WꢀC(R)–PPh2)(BF4) as
well as h2-arsinocarbene complexes of tungsten
¸¹¹¹¹¹¹º
(Cp(CO)2WꢀC(R)–AsPh2)(PF6) (R=Tol, Ph, Me)
In the proton-decoupled 13C-NMR spectra the for-
mer carbene carbon atoms are strongly shielded (Table
3). Within l=35 and 46 ppm they are found in the
takes place providing yellow diamagnetic h2-phos-
¸¹¹¹¹
phino-(Cp(CO)(PMe3)(CF3COO/CCl3COO)W–C(H)-
¹¹¹º
(R)–PPh2)(BF4) an¸d¹¹h2¹-a¹r¹si¹no¹m¹eºthanide complexes
(Cp(CO)2(CF3COO)W–C(H)(R)–AsPh2)(PF6) in high
yields (Scheme 2).
range of well-known cationic phosphoranylidene com-
¸¹¹¹¹¹¹¹¹¹º
plexes of tungsten (Cp(CO)(PMe3)W–C(PMe3)(R)–P-
Ph2)(BF4) [13] (l=7.8 ppm) and tungsta-phospha-bicy-
clo(1.1.0)butanone complexes like (Cp(MeNC)(PMe3)-
In both type of complexes the proton of the acetic
acid is located at the less nucleophilic carbene carbon
atom. Therefore the (1,2)-addition reaction is accompa-
nied probably by a significant ‘polarity reversal’ at the
metal carbene carbon unit that could be induced by the
electron-rich acetate ligand.
¸¹¹¹¹¹¹¹¹¹º
¸¹¹¹º
W–C(O)–C(Ph)–PPh2)(PF6) [18] (l=6.2 ppm). The
possible formation of diastereomeric h2-phosphi-
nomethanide complexes which formally result from the
different side attack of the proton to the prochiralic
carbene carbon atom is not observed in the NMR
studies, not even with temperature depending dynamic
NMR investigations. Therefore, we suppose a not ex-
tensively studied conversion of both diastereomeric
products via intramolecular rearrangements (see X-ray
section below).
3. Spectroscopic investigations
The IR spectra (Table 1) of 3a–4b and 5c in
dichloromethane exhibit in the region of 1998–2092
Scheme 2.

122
T. Lehotkay et al. / Journal of Organometallic Chemistry 583 (1999) 120–125
Table 2
1H-NMR spectra of 3a–5c in CDCl3 (multiplicity and coupling constants in brackets)
C6H4/5
C5H5
C–H
C–CH3
P(CH3)3
3a
3b
3c
4b
6.51–7.65
(14, m)
6.13
(5, s)
2.94
2.32
(3, s)
1.50
(1, dd, 2.9a, 2.4b)
(9, d, 10.3a)
6.64–7.66
(15, m)
6.16
(5, s)
2.96
–
1.51
(1, dd, 2.9a, 2.4b)
(9, d, 10.3a)
7.26–7.56
(10, m)
6.13
(5, s)
2.89
(1, m)
2.18
1.78
(3, d, 7.4b)
(9, d, 10.1a)
6.21–7.67
(15, m)
6.21
(5, s)
3.01
(1,s)
–
1.55
–
(9, d, 9.9a)
5c
6.64–7.67
(14, m)
6.39
(5, s)
2.81
(1, s)
2.38
(3, s)
a 2J(31P–1H).
b 3J(31P–1H).
The chemical shifts as well as the corresponding
tation (32%) with respect to the position of the acetic
anion.
intramolecular spin–spin interactions in the proton de-
coupled phosphorus NMR spectra of 3a–4b confirm
the assigned structure with a W–P–C ring system
(Table 4). The significant strong shielding of the phos-
phorus atom (l= −31.3 and −35.2 ppm) and the
4. Experimental details
1
small metal–phosphorus coupling constants J(183W–
Standard inert-atmosphere techniques were used for
the manipulation of all reagents and reaction products.
All solvents were dried according to conventional meth-
ods and stored under nitrogen over molecular sieves (4
31P) of the endocyclic phosphorus atoms within
163–165 Hz are in agreement with three-membered
metal–phosphorus–carbon ring systems [13,19–21]
¸¹¹¹¹¹¹º
˚
A). IR spectra were recorded on a Perkin–Elmer FT-
(e.g. (Cp(CO)2 WꢀC(Ph)–PPh2)(PF6): l=−114.4 ppm,
JR 1600 spectrometer. H-, 13C-, and 31P-NMR spectra
1
¸¹¹¹¹¹
1J(183W – 31P) = 113 Hz, (Cp(CO)(PMe3)W–C(Me)-
¹¹¹¹¹º
were taken in CDCl3 and CD2Cl2 on a Jeol JNM-GX
270 (1H, 270.27: 13C, 67.94; 31P, 109.37 MHz) spectrom-
eter. Chemical shifts are quoted as l in ppm with
respect to the deuterated solvents (13C) and its residual
proton resonances (1H), and to aqueous 85% H3PO4 for
31P-NMR, respectively. Mass spectra were recorded on
a Finnigan MAT90 spectrometer (molecular mass rela-
tive to 184W). The starting materials 1a–c [24] and 2
[22] were prepared as described in the literature.
CF3COOH and CCl3COOH were commercial products
from Aldrich (Scheme 3).
(PMe3)–PPh2)(PF6) l= −1.6 ppm, 1J(183W–31P)=
171 Hz). With the more deshielded exocyclic PMe3
ligand (l= −26.1 to −26.5 ppm) both signals split
2
into a doublet due to J(31P–31P) interactions.
The X-ray single crystal structure determinations of
3a (Fig. 1) and 5c (Fig. 2) display the tungsten atom in
both complexes in a distorted octahedral ligand sphere.
The cyclopentadienyl, the trimethylphosphine and the
carbonyl ligand in 3a as well as the cyclopentadienyl
and the two carbonyl functions in 5c are in a facial
arrangement.
The W(1)–C(4) (231.8(11) pm), W(1)–P(1) (240.4(3)
pm) and the P(1)–C(4) (173.9(11) pm) bond lengths
(Tables 5 and 6) within the W–P–C ring as well as the
W(1)–C(3) (234.0(5) pm), W(1)–As(1) (250.47(7) pm)
and the As(1)–C(3) (190.7(6) pm) bond distances
within the W–As–C ring are typical for single bonds
4.1. Synthesis of (Cp(CO)(PMe3)(CF3COO)-
W–C(H)(Me)–PPh2)(BF4) (3a)
¸¹¹¹¹¹¹¹¹º
To a solution of 0.37 g (0.46 mmol) of 1a in 10 ml
dichloromethane was added 0.04 ml (0.52 mmol) of
trifluoroacetic acid at −10°C. The solution was stirred
for 5 h at room temperature. Recrystallization from
dichloromethane/diethylether afforded a yellowish mi-
crocrystalline powder. Yield 0.28 g (80%). Element.
Anal. Found: C, 38.55, H, 4.00, W, 24.08.
C25H28BF7O3P2W. Calc.: C, 39.20, H, 3.68, W, 24.00%.
MS (FAB): 679 (K)+, 603 (K–PMe3)+, 575 (K–CO–
and comparable to those described in literature [22]
¸¹¹¹¹¹¹¹¹¹¹º
(e.g.
(Cp(CO)(PMe3)W–C(Me)(PMe3)–PPh2)(PF6)
W–C: 234.7 pm, W–Pcycle: 238.2 ppm, Pcycle–C: 178.3
ppm (13), Cp(CO)¸W¹–¹S¹–A¹ºs (tBu)2 W–As: 254.7 pm
[23].
We note that in 3a the added proton is located in a
favored syn-orientation (68%) as well as in an anti-orien-

T. Lehotkay et al. / Journal of Organometallic Chemistry 583 (1999) 120–125
123
Table 3
13C{1H}-NMR spectra of 3a–5c in CD2Cl2 (multiplicity and coupling constants in brackets)
3a
3b
3c
4b
5c
W–CO
214.8 (d, 4.6b)
214.5 (d, 4.6b)
217.0
212.7 (d, 4.7b)
202.6
CF3COO
CCl3COO
C6H4/5
CF3COO
CCl3COO
C5H5
W–C–H
CH3
P(CH3)3
162.3 (q, 38.6d)
162.4 (q, 38.6d)
(q, 38.6d)
–
–
–
166.2
121.9–137.4
–
118.9
92.7
46.8
–
124.8–137.7
124.6–136.9
129.5–135.7
n.f.
123.8–139.1
115.2
–
94.9
49.6
20.9
–
113.8 (q, 289.6c)
113.8 (q, 289.6c)
–
92.5
–
92.5
–
92.0
46.3 (dd, 8.3a,b
20.7
)
46.2 (dd, 8.3a, 7.4b)
35.3 (11.2a)
29.5
–
–
16.2 (d, 33.1a)
16.2 (d, 33.1a)
16.6 (d, 26.8a)
16.4 (d, 34.2a)
a 1J(31P–13C).
b 2J(31P–13C).
c 1J(19F–13C).
d 2J(19F–13C).
PMe3)+, 565 (K–CF3COOH)+, 489 (K–CO–PMe3–
CF3COOH)+.
4.5. Synthesis of (Cp(CO)(PMe3)(CCl3COO)-
W–C(H)(Tol)–AsPh2)(BF4) (4c)
¸¹¹¹¹¹¹¹¹¹º
To a solution of 0.42 g (0.54 mmol) of 2c in 10 ml
dichloromethane was added the amount of 0.05 ml
(0.65 mmol) of trifluoroacetic acid at −50°C. The
solution was stirred for 2 h at room temperature.
Recrystallization from dichloromethane/diethylether
afforded a yellowish brown microcrystalline powder.
Yield 0.37 g (80%). Element. Anal. Found: C, 40.58,
H, 3.23. C29H23AsF7O4PW. Calc.: C, 40.56, H, 2.70%.
MS (FAB): 751 (K)+, 723 (K–CO)+, 695 (K–2CO)+,
609 (KCO–CF3COOH)+.
4.2. Synthesis of (Cp(CO)(PMe3)(CF3COO)-
W–C(H)(Ph)–PPh2)(BF4) (3b)
¸¹¹¹¹¹¹¹¹º
By the method used in Section 4.1, 0.41 g (0.47
mmol of 1b and 0.04 ml (0.52 mmol of trifluoroacetic
acid provides the yellow product25
3b. Yield: 0.35 g (90%). Element. Anal. Found: C,
43.03, H, 3.80, W, 21.17. C30H30BF7O3P2W. Calc.: C,
43.47, H, 3.65, W, 22.21%. MS (FAB): 741 (K)+,
665 (K–PMe3)+, 637 (K–CO–PMe3)+, 627
(KCF3COOH)+, 523 (K–CO–PMe3–CF3COOH)+.
4.6. X-ray structure determination of 3a and 5c
4.3. Synthesis of (Cp(CO)(PMe3)(CF3COO)-
W–C(H)(Tol)–PPh2)(BF4) (2c)
X-ray crystallographic data (Table 7) were collected
¸¹¹¹¹¹¹¹¹º
by
a
Siemens P4 diffractometer with graphite-
monochromatized Mo–Ka radiation (u=71.073 pm).
The unit cell parameters were determined and refined
from 25 (3a) and 29 (5c) randomly selected reflections,
obtained by P4 automatic routines. Data were mea-
sured via v-scan and corrected for Lorentz and polar-
This compound was prepared analogously to 3a us-
ing 0.37 g (0.42 mmol) of 1c and 0.04 ml (0.52 mmol)
of trifluoroacetic acid. Yield: 0.33 g (94%). Element.
Anal. Found: C, 43.77, H, 3.96, W, 21.77.
C31H32BF7O3P2W. Calc.: C, 44.21, H, 3.83, W,
21.83%. MS (FAB): 755 (K)+, 679 (K–PMe3)+, 651
(K–CO–PMe3)+, 641 (K–CF3COOH)+, 565 (K–
CO–PMe3–CF3COOH)+.
Table 4
31P{1H}-NMR spectra of 3a–5c in CDCl3 (multiplicity and coupling
constants in brackets)
4.4. Synthesis of (Cp(CO)(PMe3)(CCl3COO)-
3a
3b
3c
4b
¸¹¹¹¹¹¹¹¹º
W–C(H)(Ph)–PPh2)(BF4) (4b)
P(CH3)3
PPh2
−26.2
−26.1
−26.5
−26.3
(d, 15.7a)
(263.8b)
(d, 17.1a)
(263.8b)
(d, 19.9a)
(262.4b)
(d, 17.4a)
(264.1b)
The procedure employed was analogous to that for
Section 4.1 using 0.16 g (0.22 mmol) of 1b and 0.06 g
(0.37 mmol) of trichloroacetic acid. Yield: 0.18 g
(92%). Element. Anal. Found: C, 40.51, H, 3.40.
C30H30BCl3F4O3P2W. Calc.: C, 41.09, H, 3.45, W,
21.83%. MS (FAB): 789 (K)+, 713 (K–PMe3)+, 627
(K–CCl3COOH)+, 599 (K–CO–CCl3COOH)+.
−35.2
−33.8
−31.1
−33.8
(d, 15.7a)
(162.6b)
(d, 17.1a)
(164.0b)
(d, 19.9a)
(165.4b)
(d, 17.4a)
(164.9b)
a 2J(31P–31P).
b 1J(183W–31P).

124
T. Lehotkay et al. / Journal of Organometallic Chemistry 583 (1999) 120–125
Table 5
Selected bond lengths (pm) and bond angles (°) for 3a
Bond lengths (pm)
W(1)–P(1)
W(1)–P(2)
W(1)–O(2)
W(1)–C(1)
W(1)–C(4)
P(1)–C(4)
240.4(3)
252.3(3)
212.2(8)
199.3(14)
231.8(11)
173.9(11)
179.3(12)
179.6(12)
O(1)–C(1)
O(2)–C(2)
O(3)–C(2)
F(11)–C(3)
F(12)–C(3)
F(13)–C(3)
C(4)–C(5)
C(2)–C(3)
113.7(13)
125(2)
123(2)
133(2)
127(2)
126(2)
155(2)
153(2)
P(1)–C(6)
P(1)–C(12)
Bond angles (°)
W(1)–P(1)–C(4)
W(1)–P(1)–C(6)
65.8(4)
124.6(4)
P(1)–C(4)–C(5)
P(2)–W(1)–O(2)
P(2)–W(1)–C(1)
P(2)–W(1)–C(4)
O(2)–W(1)–C(4)
O(2)–C(2)–O(3)
O(2)–C(2)–C(3)
O(3)–C(2)–C(3)
C(6)–P(1)–C(12)
124.0(9)
85.4(2)
83.1(3)
84.9(3)
77.4(3)
128.6(13)
113.2(14)
118(2)
W(1)–P(1)–C(12) 120.7(4)
W(1)–O(2)–C(2)
W(1)–C(4)–P(1)
W(1)–C(4)–C(5)
P(1)–W(1)–P(2)
P(1)–W(1)–O(2)
P(1)–W(1)–C(1)
P(1)–W(1)–C(4)
132.3(8)
71.1(4)
126.6(8)
127.9(10)
80.1(2)
85.8(3)
43.2(3)
Fig. 1. ORTEP plot for the molecular structure of 3a. The thermal
ellipsoids are correspondent to 30% probability (hydrogen atoms of
phenyl, cyclopentadienyl and PMe3-groups are omitted for clarity).
110.0(5)
ization effects, an empirical absorption correction,
based on v-scans, was applied. The structures were
solved by direct methods (SHELXS-86) [25] and refined
by a full matrix least-squares procedure using F2
1.5 (for methyl hydrogen atoms) higher than Ueq of the
attached carbon atoms, except for the hydrogen atom
at C(4) of 5c, which was refined isotropically with fixed
distance of 94(1) pm.
Both single crystals had disordered groups in the
asymmetric unit. For compound 3a the methyl group
has two conformations C(5a) and C(5b) with refined
occupation factors of 0.68 and 0.32. C(5a) and C(5b)
can be transferred to each other by reflection through
the plane W (1), P (1) and C(4a) (ꢀC(4b)). C(4a) and
C(4b) with occupancy 0.68 and 0.32 have equivalent
(
SHELXL-93) [26]. The function minimized was
S(w(F2o−F2o)2) with the weight defined as w−1
=
(|2(Fo2)=(xP)2+yP) and P=(Fo2 +2F2c)/3. All non-
hydrogen atoms were refined with anisotropic
displacement parameters. Hydrogen atoms were located
by difference Fourier methods, but in the refinement
they were included in calculated positions and refined
with isotropic displacement parameters 1.2 times and
Table 6
Selected bond lengths (pm) and bond angles (°) for 5c
Bond lengths (pm)
W(1)–AS(1)
W(1)–O(3)
W(1)–C(1)
W(1)–C(2)
W(1)–C(3)
As(1)–C(3)
As(1)–C(13)
As(1)–C(19)
250.47(7)
212.5(4)
202.4(6)
205.5(7)
234.0(5)
190.7(6)
192.9(6)
192.2(5)
O(1)–C(1)
O(2)–C(2)
O(3)–C(11)
O(4)–C(11)
F(7)–C(12)
F(8)–C(12)
F(9)–C(12)
C(3)–C(4)
113.5(7)
113.0(7)
127.9(6)
119.4(7)
126.8(8)
133.6(9)
129.9(8)
148.9(8)
Bond angles (°)
W(1)–As(1)–C(3)
W(1)–As(1)–C(13) 122.4(2)
W(1)–As(1)–C(19) 126.4(2)
62.3(2)
O(3)–W(1)–C(1)
O(3)–W(1)–C(2)
O(3)–W(1)–C(3)
O(3)–C(11)–O(4)
O(3)–C(11)–C(12)
C(1)–W(1)–C(2)
C(1)–W(1)–C(3)
C(2)–W(1)–C(3)
C(3)–As(1)–C(13)
C(3)–As(1)–C(19)
151.6(2)
87.8(2)
75.8(2)
127.7(6)
112.7(5)
83.0(2)
76.4(2)
82.4(2)
111.4(2)
116.4(2)
W(1)–O(3)–C(11)
W(1)–C(3)–As(1)
W(1)–C(3)–C(4)
As(1)–W(1)–O(3)
As(1)–W(1)–C(1)
As(1)–W(1)–C(2)
As(1)–W(1)–C(3)
As(1)–C(3)–C(4)
125.7(4)
71.5(2)
129.0(4)
76.58(9)
88.2(2)
128.4(2)
46.20(13)
128.2(4)
Fig. 2. ORTEP plot for the molecular structure of 5c. The thermal
ellipsoids are correspondent to 30% probability (only the hydrogen
atom at C(3) is shown for clarity).
C(13)–As(1)–C(19) 108.1(2)

T. Lehotkay et al. / Journal of Organometallic Chemistry 583 (1999) 120–125
125
Further details of the crystal structure investigation
are available from the Fachinformationszentrum Karls-
ruhe, D-76344 Eggenstein-Leopoldshafen (Germany),
on quoting the depository number CSD-408821 (3a)
and CSD-408821 (5c), the names of authors, and the
journal citation.
Scheme 3.
Acknowledgements
coordinates and temperature parameters to calculate
the disordered hydrogen atom. For compound 5c the
fluorine atoms of the anion PF6− have two possible
positions F(1)–F(6) and F(1a)–F(6a) with refined occu-
pancy of 0.57 and 0.43.
The authors 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.
Table 7
Crystal data and structure refinement for 3a and 5c
References
Empirical formula
C25H28BF7O3P2 C29H23AsF9O4
W×0.5CH2Cl2 PW×C4H4O
[1] E.O. Fischer, G. Kreis, C. G. Kreiter, J. Mu¨ller, G. Huthner, H.
Lorenz, Angew. Chem. 85 (1973) 618; Angew. Chem. Int. Ed.
Engl. 12 (1973) 564.
[2] L.J. Guggenberger, R.R. Schrock, J. Am. Chem. Soc. 97 (1975)
2935.
[3] P.R. Sharp, S.J. Holmes, R.R. Schrock, M.R. Churchill, H.J.
Wasserman, J. Am. Chem. Soc. 103 (1981) 965.
[4] R.R. Schrock, Acc. Chem. Res. 19 (1986) 342.
[5] H.P. Kim, R.J. Angelici, Adv. Organomet. Chem. 27 (1987) 51.
[6] K.H. Do¨tz, H. Fischer, P. Hofmann, F.R. Kreissl, U. Schubert,
K. Weiss, Transition Metal Carbene Complexes, VCH Verlag,
Weinheim, 1983.
[7] C.R. Clark, S.V. Hoskins, T.C. Jones, W.R. Roper, J. Chem.
Soc. Chem. Commun. (1983) 719.
[8] C.P. Casey, P.C. Vosojpka, F.R. Askham, J. Am. Chem. Soc.
112 (1990) 3713.
[9] W. Schu¨lt, N. Ullrich, F.R. Kreissl, J. Organomet. Chem. 408
(1991) C5.
Formula weight
808.54
964.29
(g mol−1
)
Crystal form/color
Temperature (K)
Radiation
Yellow plates
213(2)
Yellow plates
218(2)
Mo–Ka
Mo–Ka
(71.073 pm)
Monoclinic
(71.073 pm)
Monoclinic
Crystal system
Space group
Unit cell dimensions
a (pm)
b (pm)
c (pm)
P21/c (No. 14) P21/c (No. 14)
1029.7(4)
2430.6(3)
1355.1(1)
109.19(12)
3.2031(13)
4
1500.3(3)
1185.6(2)
2091.6(3)
104.20(1)
3.6068(11)
4
i (°)
V (nm3)
Z
Dcalc. (g cm−3
)
1.677
1.776
[10] J. Ostermeier, W. Schu¨tt, C.M. Stegmair, N. Ullrich, F.R.
Kreissl, J. Organomet. Chem. 464 (1993) 77.
[11] F.R. Kreissl, C.M. Stegmair, Chem. Ber. 124 (1991) 2747.
[12] F.R. Kreissl, M. Wolfgruber, Z. Naturforsch. 43b (1988) 1307.
[13] J. Ostermeier, W. Hiller, F.R. Kreissl, J. Organomet. Chem. 491
(1995) 283.
[14] F.R. Kreißl, H. Keller, Angew. Chem. 98 (1986) 924.
[15] J. Ostermeier, W. Schu¨tt, F.R. Kreissl, J. Organomet. Chem. 436
(1992) C17.
[16] Th. Lehotkay, F.R. Kreissl, (1998), unpublished results.
[17] F.R. Kreissl, F.X. Mu¨ller, D.L. Wilkinson, G. Mu¨ller, Chem.
Ber. 122 (1989) 289.
[18] Th. Lehotkay, K. Wurst, P. Jaitner, F.R. Kreissl, J. Organomet.
Chem. 553 (1998) 103.
Absorption coefficient
(mm−1
F(000)
3.856
4.242
)
1580
1872
Crystal dimensions (mm3) 0.3×0.21×0.19 0.3×0.3×0.14
Theta range for data
collection (°)
Index ranges
3.13–20.49
2.57–21.00
05h59,
05k525,
−135l510
3092
2978
[Rint=0.0268]
2292
05h515,
−15k512,
−225l521
4172
3839
[Rint=0.0328]
2863
Reflections collected
Independent reflections
Reflections observed
[I\2|(I)]
Absorption correction
Refinement method
[19] Th. Lehotkay, K. Wurst, P. Jaitner, F.R. Kreissl, J. Organomet.
Chem. 523 (1996) 105.
C-scan
Full-matrix
least-squares on least-squares on
C-scan
Full-matrix
[20] P.E. Garrou, Chem. Rev. 81 (1981) 229.
[21] P.S. Pregosin, R.W. Kunz, 31P and 13C-NMR of Transition
Metal Phosphine Complexes, Springer, Berlin, 1979.
[22] F.R. Kreissl, Th. Lehotkay, C. Ogric, E. Herdtweck,
Organometallics 16 (1997) 1875.
[23] W. Malisch, M. Luksza, Z. Naturforsch. 36b (1981) 1580.
[24] M. Wolfgruber, F.R. Kreissl, J. Organomet. Chem. 349 (1988)
C4.
[25] Sheldrick G.M., SHELXS-86: Program for Crystal Structure Solu-
tions, Go¨ltingen, 1986.
[26] Sheldrick G.M., SHELXL-93: Program for the Refinement of
Crystal Structures, Go¨ltingen, 1993.
F2
Data/restraints/parameters 2786/0/391
Goodness-of-fit on F2
1.066
Final R indices [I\2|(I)] R1=0.0362,
wR2=0.0796
F2
3557/1/511
1.040
R1=0.0360,
wR2=0.0636
R1=0.0648,
wR2=0.0788
R indices (all data)
R1=0.0582,
wR2=0.0905
564 and −492 477 and −395
Largest difference peak
and hole (e nm−1
)