Facile synthesis of pentacarbonyltungsten(0) complexes with oxaphosphirane ligands

Article abstract of DOI:10.1002/zaac.200900063

Facile synthesis of tungsten(O) complexes of the type [{(R ¹PCH(R²)-O)}W(CO)₅] 7a-g (R¹ = C₅Me₅) and. 8a - g (R¹ = CH(SiMe ₃)₂) using transient Li/Cl phosph

Full text of DOI:10.1002/zaac.200900063

ARTICLE
DOI: 10.1002/zaac.200900063
Facile Synthesis of Pentacarbonyltungsten(0) Complexes with Oxaphosphirane
Ligands
[a]
[a]
[a]
[a]
´
Rainer Streubel,* Maren Bode, Janaina Marinas Perez, Gregor Schnakenburg,
Jörg Daniels,[a] Martin Nieger,[b] and Peter G. Jones[c]
Dedicated to Professor Edgar Niecke on the Occasion of His 70th Birthday
Keywords: Phosphorus heterocycles; Phosphanylidenoid complexes; Oxaphosphirane complexes; Tungsten
Abstract. Facile synthesis of tungsten(0) complexes of the type
[{(R1PCH(R2)ϪO)}W(CO)5] 7aϪg (R1 ϭ C5Me5) and 8aϪg (R1 ϭ
CH(SiMe3)2) using transient Li/Cl phosphanylidenoid tungsten(0) tures of complexes 7b,dϪg and 8b,d are presented.
complexes 4, 5 and carbonyl derivatives 6aϪg is reported; further-
more, for all complexes NMR, IR spectroscopic, mass spectro-
metric investigations and, in addition, single-crystal X-ray struc-
T
U
vestigations [7] predict their existence, although some
rearrangements might occur [7, 8]. In 1994, we described a
new route to oxaphosphirane complexes (II) using ther-
mally induced ring cleavage of a 2H-azaphosphirene com-
Introduction
The chemistry of oxaphosphiranes involving phosphorus
with high coordination number dates back to 1978, when
the first synthesis of a σ4λ5-oxaphosphirane derivative was
plex (III) in the presence of an aldehyde [9] or a ketone [10]
described by Röschenthaler and Schmutzler using Niecke’s
derivative. In the latter case a side reaction to a benzo[c]-
iminophosphane and hexafluoroacetone [1]. In 1982, the in-
1,2-oxaphospholane complex occurred. A new facile proto-
termediacy of σ4λ5-oxaphosphirane P-oxide derivatives in
col for the synthesis of complexes II was reported recently
ring expansion reactions was claimed by Bartlett [2]. In
that utilized the reaction of easily available complexes IV,
1988, some NMR evidence was provided by Boisdan and
tert-butyllithium and aldehydes [11].
Barrans, who investigated a monomer-dimer equilibrium of
a σ5λ5-oxaphosphirane [3]. Although recent theoretical in-
vestigations [4] predict easy decomposition into phosphane
and carbonyl derivatives, further evidence for the existence
of σ5λ5-oxaphosphiranes was gained by Butenschön [5]. In
1990, Mathey’s discovery that σ3λ3-oxaphosphirane com-
plexes (II) can be obtained through epoxidation of phos-
phaalkene complexes (I) with m-CPBA was a further break-
through (Scheme 1) [6]. Although non-ligated σ3λ3-oxa-
phosphirane derivatives are still unknown, theoretical in-
* Prof. Dr. R. Streubel
Fax: ϩ49-228-735345
E-Mail: r.streubel@uni-bonn.de
[a] Institut für Anorganische Chemie
Rheinische Friedrich-Wilhelms-Universität Bonn
Scheme 1. Synthetic routes to oxaphosphirane complexes II (R de-
Gerhard-Domagk-Str. 1
notes ubiquitous organic substituents. [M] denotes a W(CO)5
53121 Bonn, Germany
group).
[b] Laboratory of Inorganic Chemistry
Department of Chemistry
University of Helsinki
It should be pointed out that oxaphosphirane chemistry
P.O. Box 55 (A.I. Virtasen aukio 1)
is still largely undeveloped, which might be attributed to
the restricted accessibility. The first example of a C,O bond
cleavage reaction was reported very recently, showing that
FI-00014 Helsinki, Finland
[c] Institut für Anorganische und Analytische Chemie
Technische Universität Braunschweig
Hagenring 30
38106 Braunschweig, Germany
[{Me5C5P
T
CH(Ph)ϪO
U
}W(CO)5] react thermally with alde-
Z. Anorg. Allg. Chem. 2009, 635, 1163Ϫ1171
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 1163

´
R. Streubel, M. Bode, J. Marinas Perez, G. Schnakenburg, J. Daniels, M. Nieger, P. G. Jones
ARTICLE
hydes to furnish new O,P,C-cage ligands [12]. Furthermore, Nevertheless, some trends are becoming apparent and thus
we developed a protocol for the selective P,O bond ring can be described for the first time: complexes with oxaphos-
expansion of [{(Me3Si)2HCPTCH(Ph)ϪOU}W(CO)5] using phirane ligands that possess a PϪCp* substituent always
trifluoromethane sulfonic acid, carbonitriles and triethyl- show resonances that reveal slightly more shielded phos-
amine as base [13]. Here, we report on the synthesis of tung- phorus nuclei than those with a PϪCH(SiMe3)2 substitu-
sten(0) complexes of the type [{(R1PCH(R2)ϪO
T U)}W(CO)5] ent, and thus a Δδ of approx. 4Ϫ11 results. The tungstenϪ
7aϪg and 8aϪg using transient Li/Cl phosphanylidenoid phosphorus coupling constant magnitude lies within the
tungsten(0) complexes and aldehydes 6aϪg; furthermore, range 303 6 Hz and is virtually identical for correspond-
single-crystal X-ray structures of complexes 7b,dϪg and ing derivatives.
8b,d are presented.
Table 1. 31P{1H} NMR spectroscopic dataa) of PϪC5Me5- and
PϪCH(SiMe3)2-substituted oxaphosphirane tungsten(0) complexes
7aϪgb) and 8aϪgc).
Results and Discussion
Synthesis
Reaction of dichloro(organo)phosphane complexes 1
(R1 ϭ C5Me5) [14] and 2 [R2 ϭ CH(SiMe3)2] [15] with tert-
butyllithium or of monochloro(organo)phosphane 3 [R ϭ
C5Me5 (ϭCp*)] [16] with LDA at low temperature in the
presence of 12-crown-4 and aldehydes 6aϪg yielded selec-
tively oxaphosphirane complexes 7a [12], 7bϪg and 8a [9],
8bϪe and 8g [11] (Scheme 2). As our investigations showed
[17], Li/Cl phosphanylidenoid tungsten(0) complexes 4 and
5 are transiently formed by chloro-lithium exchange in com-
plexes 1 and 2 or deprotonation/lithiation of 3.
7/8
R2
δ (31P{1H}) (Η1JW, P Η)
δ (31P{1H}) (Η1JW, P Η)
a
b
c
d
e
f
Ph
31.6 (309.0)
32.1 (307.7)
30.9 (306.4)
11.0 (298.8)
24.7 (298.8)
22.8 (298.8)
23.0 (297.5)
38.2 (307.7)
41.0 (306.6)
39.2 (305.5)
22.5 (298.8)
31.9 (298.8)
27.7 (302.6)
29.0 (299.8)d)
o-Tol
o-Anis
tBu
iPr
nPr
Me
g
a) J values are given in Hz; b) in C6D6; c) in CDCl3; d) only obser-
ved in reaction solution (Et2O).
Table 2. Selected 13C{1H} NMR spectroscopic dataa) of
PϪC5Me5- and PϪCH(SiMe3)2-substituted oxaphosphirane tung-
sten(0) complexes 7aϪgb) and 8aϪgc).
Scheme 2. Synthesis of oxaphosphirane complexes 7, 8aϪg through
reaction of transiently formed Li/Cl phosphanylidenoid comple-
xes 4,5.
Complexes 7aϪg and 8aϪf were isolated using column
chromatography at low temperature and neutral aluminum
oxide as solid phases or Ϫ if 3 was used as phosphanyl-
idenoid precursor Ϫ by extraction and washing the residue
with n-pentane at low temperature. All complexes were fully
characterized by NMR and IR spectroscopy and mass spec-
trometry.
7/8 R2
δ (13C{1H}) (ΗJ(P,C)Η)
C3 C4
δ (13C{1H}) (ΗJP,CΗ)
C3 C4
a
b
c
d
e
f
Ph
o-Tol
55.5 (17.5) 63.0 (10.0) 57.9 (27.5) 30.5 (18.8)
54.9 (15.5) 63.1 (10.1) 57.9 (24.5) 32.7 (20.3)
o-Anis 54.7 (20.2) 64.3 (10.0) 54.7 (28.2) 30.4 (20.2)
tBu
iPr
nPr
Me
63.0 (19.1) 62.6 (7.4)
60.7 (20.0) 61.9 (8.1)
55.2 (20.7) 61.8 (7.8)
51.2 (22.0) 61.8 (7.8)
67.1 (28.5) 33.6 (15.4)
62.9 (28.7) 28.7 (17.1)
57.4 (30.7) 28.5 (16.4)
Unfortunately, complex 8g was only identified by 31P
NMR spectroscopy because decomposition occurred dur-
ing column chromatography.
g
Ϫd)
Ϫd)
a) J values are given in Hz; b) in C6D6; c) in CDCl3; d) not measured.
The 13C{1H} NMR spectroscopic data of complexes
7aϪg and 8aϪf reveal a similar trend for the chemical shifts
of the C3-carbon atoms (Table 2). Interestingly, here the
Discussion of NMR Spectroscopic and Mass Spectrometric
Results
Complexes 7aϪg and 8aϪg display 31P NMR spectro- phosphorusϪcarbon coupling constant magnitudes differ
scopic data typical for this class of compounds (Table 1). significantly and those of the PϪCH(SiMe3)2 derivatives
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Z. Anorg. Allg. Chem. 2009, 1163Ϫ1171

Facile Synthesis of Pentacarbonyltungsten(0) Complexes
are always larger, which is also the case for the couplings
with the external C4-carbon atom. The phosphorusϪ
carbon couplings are significantly larger than those of other
three-membered, saturated phosphorus heterocyclic ligands
such as phosphiranes [18] and azaphosphiridines bound to
pentacarbonyl-tungsten(0) [19]; the latter is currently under
investigation by us [20]. One more aspect deserves com-
ment: there is a clear trend in the aliphatic series showing
that the C3 atom becomes more deshielded (g > f > e > d).
One might be tempted to interpret this in terms of an
increase in steric demand of the alkyl substituent
(tBu > iPr > nPr > Me) but as the solid-state structures
reveal (see next chapter and Table 3 and Table 4) there is
no trend in the structural data that parallels (and thus could
support) the assumption of an increasing van-der-Waals re-
pulsion in this series Ϫ and thus (pure) electronic effects
are operative.
The mass spectrometric experiments (EI) revealed the
molecular ion peak of all complexes 7aϪg and 8aϪf with
relative intensities of ca. 5Ϫ20 %. For complexes 7aϪg two
fragmentation pathways were observed, starting always
with oxaphosphirane ring fragmentation and formation of
the neutral aldehydes and [{(OC)5WPC5Me5}·ϩ] (m/z 490)
in the first step. Then either carbonyltungsten radical-
cations of various compositions (with regard to the coordi-
nation number of CO) are formed, which still have the
Cp* substituent or do not have a Cp* substituent but
instead a larger number of carbon monoxide ligands. In all
spectra the base peak is given by m/z 406 assigned to
[{(OC)2WPC5Me5}·ϩ], which then yields the fragment
m/z 271 assigned to [{(OC)2WP}·ϩ]. In the case of
complexes 8aϪf the oxaphosphirane ring fragmentation
dominated, thus forming m/z 514, assigned to
[(CO)5WPCH(SiMe3)2·ϩ]. Here, the base peak (m/z 486)
was assigned to [(OC)4WPCH(SiMe3)2·ϩ], apparently
formed through loss of CO from the precursor.
Figure 1. Molecular structure of complex 7b in the crystal (50 %
probability level; hydrogen atoms except H1 are omitted for cla-
rity).
Crystal Structures of Complexes 7b,d؊g and 8b,d
The molecular structures of complexes 7b,dϪg and 8b,d
were unambiguously established by X-ray diffraction stud-
ies. Whereas most of the complexes crystallize triclinic
(7b,eϪg, 8b) 7d and 8d crystallize monoclinic. In the cases
of complexes 7f,g and 8b (in which 2 independent molecules
are present in the unit cell), the data for only one are pre-
sented here as the other is not significantly different (7g
and 8b) or is disordered (7f). The molecular structures are
displayed in Figures 1Ϫ7, crystallographic data are given in
Table 3 and selected bond lengths and angles are summar-
ized in Table 4. Characteristic structural features of the
three-membered ring of the oxaphosphirane complexes are
the acute endocyclic angle at phosphorus of about 52°,
which, together with three significantly different endocyclic
Figure 2. Molecular structure of complex 7d in the crystal (50 %
probability level; hydrogen atoms except H1 are omitted for cla-
rity).
˚
bonds (CϪO ca. 1.47, PϪO ca. 1.67 and PϪC ca. 1.79 A),
creates a peculiar three-membered ring arrangement. The clearly indicates the influence of oxygen bound to phos-
˚
PϪW distance is notably short (ca. 2.47 A) and is unaffec- phorus, as it is also evidenced in many acyclic phosphite-
ted by the substitution pattern of the ligand; the former type complexes. The only bond that seems to be affected by
Z. Anorg. Allg. Chem. 2009, 1163Ϫ1171
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1165

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R. Streubel, M. Bode, J. Marinas Perez, G. Schnakenburg, J. Daniels, M. Nieger, P. G. Jones
ARTICLE
Figure 5. Molecular structure of one independent molecule of com-
plex 7g in the crystal (50 % probability level; hydrogen atoms except
H6 are omitted for clarity).
Figure 3. Molecular structure of complex 7e in the crystal (50 %
probability level; main orientation 70 %; hydrogen atoms except
H1, H1Ј and H12 are omitted for clarity).
Figure 6. Molecular structure of one independent molecule of com-
plex 8b in the crystal (50 % probability level; hydrogen atoms except
H21a are omitted for clarity).
Experimental Section
All operations were performed under deoxygenated and dry argon,
using standard Schlenk techniques with conventional glassware.
Solvents were distilled from sodium wire. NMR spectroscopic data
were recorded with a Bruker Avance 300 spectrometer (13C:
75.5 MHz; 31P: 121.5 MHz) at 30 °C (7a,b,dϪg and 8aϪg) or a
Bruker DPX 500 spectrometer (13C: 125.8 MHz; 31P: 202.4 MHz)
at 25 °C (7c) using C6D6 (7aϪg) or CDCl3 (8aϪg) as solvent and
internal standard; shifts are given relative to tetramethylsilane (1H,
13C) and 85 % H3PO4 (31P). Mass spectra were recorded with a
Kratos MS 50 spectrometer (EI, 70 eV). Elemental analyses were
performed using an Elementa (Vario EL) analytical gaschromato-
Figure 4. Molecular structure of one independent molecule of com-
plex 7f in the crystal (50 % probability level; hydrogen atoms except
H1 are omitted for clarity).
the substitution pattern is the CϪO bond, which varies
˚
˚
from 1.473(3) A (7b,d) to 1.522(5) A (7f); the CϪO bond in
˚
7e is even longer [1.557(6) A] but this (most probably) is an
artifact of disorder.
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Facile Synthesis of Pentacarbonyltungsten(0) Complexes
by full-matrix least-squares on F2 (SHELXL-97 [21]). All non-hy-
drogen atoms were refined anisotropically. The hydrogen atoms, if
not found in difference density map (7b), were included in calcu-
lated positions using a riding model. Crystallographic data (exclud-
ing structure factors) for the structures reported in this paper have
been deposited with the Cambridge Crystallographic Data Centre
as supplementary publication no. CCDC-711298 (7b), CCDC-
711299 (7d), CCDC-711300 (7e), CCDC-711301 (7f), CCDC-
711302 (7g), CCDC-711303 (8b) and CCDC-711304 (8d). Copies
of the data can be obtained free of charge on application to CCDC,
12 Union Road, Cambridge CB21EZ [Fax: ϩ44-1223-336-033;
E-Mail: deposit@ccdc.cam.ac.uk].
General Procedure for the Preparation of Complexes
[{Me5C5PT U}W(CO)5] (7a؊g)
CH(R2)؊O
Protocol A (7a,e,g): To a solution of [(Me5C5PCl2)W(CO)5] (1)
(230 mg, 0.41 mmol) dissolved in diethyl ether (5 mL), 12-crown-4
(74 μL, 0.46 mmol) and afterwards benzaldehyde (a) (46 μL,
0.46 mmol), isobutyraldehyde (e) (42 μL, 0.46 mmol) or acetalde-
hyde (g) (0.03 mL, 0.5 mmol) were added. The solution was cooled
to Ϫ80 °C and a solution of tert-butyllithium in n-pentane (0.3 mL,
Figure 7. Molecular structure of complex 8d in the crystal (50 %
probability level; hydrogen atoms except H1 are omitted for cla- 0.46 mmol, 1.5 m) diluted with diethyl ether (5 mL) (Ϫ80 °C) was
rity).
added dropwise. The solutions were then stirred for 90 min while
gently warming to Ϫ20 °C. Afterwards, the solvents were removed
in vacuo (ca. 0.01 bar) and the residue was extracted with n-pen-
tane (20 mL). The product was purified by column chromatography
and the dry crude product was washed with n-pentane at Ϫ70 °C.
graph. Infrared spectra were collected with a FT-IR Nicolet 380.
Melting points were obtained with a Büchi 535 capillary apparatus.
X-ray crystallographic analysis of 7b,d؊g and 8b,d: Data were col-
lected with a Nonius-KappaCCD diffractometer at 123 K using
Mo-Kα radiation (λ ϭ 0.71073 A) (7b,dϪf and 8b,d) or a Bruker (LDA, freshly prepared from n-butyllithium and diisopropylamine,
Protocol B (7a؊d,f,g): To a solution of lithium diisopropylamide
˚
SMART diffractometer at 133 K (7g). The structures were refined
1.2 equivalents) in diethyl ether cooled to Ϫ80 °C, a solution of
Table 3. Crystallographic data of oxaphosphirane tungsten(0) complexes 7b,dϪg and 8b,d.
7b
7d
7ea)
7fb)
7gc)
8bd)
8d
R1
C5Me5
o-Tol
C5Me5
tBu
C5Me5
iPr
C5Me5
nPr
C5Me5
Me
CH(SiMe3)2
o-Tol
CH(SiMe3)2
tBu
R2
Formula
C23H23O6PW C20H25O6PW C19H23O6PW C19H23O6PW C17H19O6PW C20H27O6PSi2W C17H29O6PSi2W
Molecular weight /g·molϪ1 610.07
576.22
1.00 ϫ 0.40
ϫ 0.20
monoclinic,
C2/c
562.20
0.40 ϫ 0.30
ϫ 0.20
562.20
0.60 ϫ 0.30
ϫ 0.2
534.14
0.20 ϫ 0.12
ϫ 0.08
634.04
0.32 ϫ 0.20
ϫ 0.16
600.39
0.36 ϫ 0.32
ϫ 0.20
monoclinic
P21/n
Crystal size/mm
0.28 ϫ 0.26
ϫ 0.07
Crystal system, space group triclinic,
triclinic,
triclinic,
triclinic,
triclinic,
¯
P1
¯
¯
¯
¯
P1
P1
P1
P1
˚
a /A
10.1759(3)
10.5149(4)
13.0168(5)
112.382(2)
101.178(2)
105.456(2)
1171.14(7)
2
28.6042(10)
11.3211(4)
15.3514(5)
90
116.9660(13)
90
8.6583(2)
10.4122(2)
11.9464(3)
94.080(1)
95.639(1)
90.291(1)
1068.98(4)
2
10.7186(3)
12.7122(3)
16.9111(5)
90.1314(16)
106.0680(15)
102.4240(14)
2157.68(10)
4
9.3055(14)
13.627(2)
15.434(2)
87.147(5)
86.427(5)
89.101(5)
1950.7(5)
4
10.7196(4)
15.8421(7)
16.9897(7)
70.7067(18)
80.751(2)
78.910(2)
2657.58(19)
4
9.5099(3)
18.8095(6)
13.6649(5)
90
91.237(2)
90
˚
b /A
˚
c /A
Ͱ /°
β /°
γ /°
3
˚
V /A
4430.8(3)
8
2443.76(13)
4
Z
2θmax /°
55
70
22464
(9384)
0.0583
5.317
55
10643
(4788)
0.0388
5.508
58
29512
(11156)
0.0524
5.457
61
45983
(11802)
0.0342
6.031
56
30787
(12469)
0.0599
4.529
56
18592
(5796)
0.0518
4.917
Collected (indpt) reflections 20461
(5251)
Rint
0.0504
5.035
μ /mmϪ1
Refined parameters
R1 (for I > 2σ (I))
wR2 (for all data)
max./min. residual electron
372
262
247
520
0.0336
0.0821
3.220/
471
602
0.0387
0.0833
1.400/
253
0.0228
0.0520
1.233/
Ϫ1.824
0.0281
0.0653
1.740/
0.0288
0.0693
2.379/
0.0230
0.0522
1.109/
0.0287
0.0556
0.984/
Ϫ3
˚
density / e·A
Ϫ2.385
Ϫ1.898
Ϫ1.674
Ϫ1.155
Ϫ1.692
Ϫ1.770
a) Disordered structure, main orientation 70 %; b) two independent molecules, structure of a second disordered molecule: main orienta-
tion: 56 %; c) two independent molecules; d) two independent molecules, one molcule of n-pentane in the unit cell.
Z. Anorg. Allg. Chem. 2009, 1163Ϫ1171
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ARTICLE
Table 4. Selected structural data of oxaphosphirane tungsten(0) complexes 7b,dϪg and 8b,d.
7b
7d
7ea)
7fb)
7gc)
8bd)
8d
R1
R2
C5Me5
o-Tol
C5Me5
tBu
C5Me5
iPr
C5Me5
nPr
C5Me5
Me
CH(SiMe3)2
o-Tol
CH(SiMe3)2
tBu
˚
Bond lengths /A
WϪP
PϪO
2.465(6)
1.672(2)
1.799(3)
1.473(3)
1.488(4)
2.488(5)
1.672(2)
1.787(2)
1.473(3)
1.526(3)
2.463(1)
1.714(4)
1.847(4)
1.557(6)
1.492(6)
2.486(1)
1.682(3)
1.793(4)
1.522(5)
1.504(5)
2.469(1)
1.666(2)
1.786(3)
1.490(3)
1.498(4)
2.459(2)
1.667(4)
1.805(5)
1482(6)
1.815(5)
2.480(8)
1.668(2)
1.784(3)
1.487(4)
1.811(3)
PϪC(ring)
C(ring)ϪO(ring)
C(ring)ϪC(R2)
Bond angles /°
C(ring)ϪPϪO
PϪC(ring)ϪO
C(ring)ϪOϪP
50.1(1)
60.4(1)
69.5(1)
50.3(1)
60.8(1)
69.0(1)
52.6(2)
60.9(2)
66.5(2)
51.8(2)
60.3(1)
67.9(1)
51.0(1)
60.3(1)
68.7(1)
50.5(2)
59.9(2)
69.6(3)
50.88(1)
60.6(2)
68.7 (2)
a) Disordered structure, main orientation 70 %; b) two independent molecules, structure of a second disordered molecule: main orienta-
tion: 56 %; c) two independent molecules; d) two independent molecules, one molcule of n-pentane in the unit cell.
[{Me5C5P(H)Cl}W(CO)5] (3), 1 equivalent of 12-crown-4 and 1 [{Me5C5P
T
CH(o-tolyl)-O
U
}W(CO)5] (7b): Yield: 420 mg (73 %) (B);
equivalent of the appropriate aldehyde in diethyl ether was slowly
added (volumes and quantities see Table 5). The solution was
stirred for 2 h while gently warming to Ϫ20 °C. Afterwards, the
solvents were removed in vacuo (ca. 0.01 bar) and the residue was
extracted with n-pentane (15Ϫ40 mL). The raw product was
washed carefully with n-pentane at Ϫ70 °C.
m.p. 108Ϫ9 °C (decomp); C23H23O6PW (610.07 g·molϪ1): calc: C
1
45.27, H 3.80 %; exp: C 45.22, H 3.97 %. H NMR: δ ϭ 0.65 (d,
P,H ϭ 11.3 Hz, 3 H, Cp*-C1-CH3), 1.41Ϫ1.45 (mc, 6 H, Cp*-CH3),
1.52 (s, 3 H, Cp*-CH3), 1.75 (s, 3 H, Cp*-CH3 or Ar-CH3), 1.92 (s,
J
3 H, Cp*-CH3 or Ar-CH3), 3.92 (s, 1 H, POC-H), 6.72 (d, JH,H
6.99 Hz, 1 H, Ar), 6.81Ϫ6.91 (mc, 2 H, Ar), 7.40 (d, JH,H
ϭ
ϭ
6.99 Hz, 1 H, Ar); 13C{1H} NMR: δ ϭ 9.9 (d, JP,C ϭ 3.0 Hz,
Table 5. Reaction conditions for the synthesis of 7aϪg.
Cp*-CH3), 10.0 (d, JP,C ϭ 1.8 Hz, Cp*-CH3), 10.3 (d, JP,C
1.2 Hz, Cp*-CH3), 10.5 (d, JP,C ϭ 1.8 Hz, Cp*-CH3), 12.2 (d,
JP,C ϭ 4.8 Hz, Cp*-C1-CH3), 17.8 (s, Ar-CH3), 54.9 (d, JP,C
ϭ
7
R
LDA
3: m /mg
12-c-4 6aϪg Et2O /mL
ϭ
n / mmol (n /mmol) V /μL V /μL VLDA/VR
15.5 Hz, POCH), 63.1 (d, JP,C ϭ 10.1 Hz, Cp*-C1), 125.0 (d, JP,C ϭ
4.8 Hz, Ar), 125.1 (d, JP,C ϭ 2.4 Hz, Ar), 127.1 (d, JP,C ϭ 2.4 Hz,
Ar), 128.8 (d, JP,C ϭ 2.4 Hz, Ar), 132.0 (d, JP,C ϭ 8.3 Hz, Cp* or
Ar), 132.1 (s, Cp* or Ar), 134.2 (d, JP,C ϭ 1.8 Hz, Cp* or Ar),
136.5 (s, Cp* or Ar), 141.0 (d, JP,C ϭ 1.2 Hz, Cp*), 142.8 (d, JP,C ϭ
a
b
c
d
f
Ph
o-Tol
0.5
1.0
221 (0.42) 68
442 (0.84) 136
442 (0.84) 136
442 (0.84) 136
221 (0.42) 68
246 (0.47) 76
43
98
5/5
10/10
10/10
10/10
5/5
o-Anis 1.0
115a)
190
38
tBu
nPr
Me
1.0
0.5
0.6
2
1
6.0 Hz, Cp*), 192.8 (dSat, JP,C ϭ 8.3, JW, C ϭ 125.2 Hz, cis-CO),
g
30
2/2
194.2 (d, JP,C ϭ 37.6 Hz, trans-CO); 31P{1H} NMR: δ ϭ 32.1
2
a) 5c: m /mg.
(sSat,
1JW, P ϭ 307.7 Hz). MS: m/z (%) ϭ 610 (19) [M·ϩ], 526
(13) [(M-3CO)·ϩ], 490 (12) [{(OC)5WPCp*}·ϩ], 406 (25)
[{(OC)2WPCp*}·ϩ], 299 (3) [{(OC)3WP}·ϩ], 135 (42) [(Cp*)·ϩ],
134 (100) [(Cp*-H)·ϩ], 119 (28) [(Cp*-Me-H)·ϩ], 105 (7)
[(Cp*-2Me)·ϩ], 91 (3) [(Cp*-2Me-CH2)·ϩ]. IR (KBr; ν˜(CO)): ν˜ ϭ
[{Me5C5P
T
CH(Ph)؊O}W(CO)5] (7a) [12]: Yield: 54 mg (22 %) (A)
U
or 182 mg (73 %) (B); m.p. 103 °C (decomp.); C22H21O6PW (596.21
g·molϪ1): calc: C 44.32, H 3.55 %; exp: C 44.39, H 3.69 %; Selected
1
3
1934 (s), 1990 (s), 2073 (s) cmϪ1
.
NMR spectroscopic data: H NMR: δ ϭ 0.83 (d, JP,H ϭ 11.3 Hz,
3 H, Cp*-C1-CH3), 1.65 (mc, 6 H, Cp*-CH3), 1.68 (s, 3 H,
Cp*-CH3), 1.93 (s, 3 H, Cp*-CH3), 4.23 (s, 1 H, POC-H),
[{Me5C5PCH(o-anisyl)-O}W(CO)5] (7c): Yield: 391 mg (74 %) (B);
T
U
7.05Ϫ7.37 (m, 5 H, Ph); 13C{1H} NMR: δ ϭ 9.5 (d, JP,C ϭ 3.2 Hz, m.p. 78Ϫ80 °C (decomp); C23H23O7PW (626.24 g·molϪ1): calc: C
Cp*-CH3), 10.1 (d, JP,C ϭ 2.3 Hz, Cp*-CH3), 10.2 (d, JP,C
ϭ
44.11, H 3.70 %; exp: C 43.46, H 4.03 %. 1H NMR (500.1 MHz,
1.3 Hz, Cp*-CH3), 10.6 (d, JP,C ϭ 1.6 Hz, Cp*-CH3), 12.0 (d, 25 °C, C6D6): δ ϭ 0.95 (d, JP,H ϭ 11.3 Hz, 3 H, Cp*-C1-CH3),
JP,C ϭ 4.8 Hz, Cp*-C1-CH3), 55.5 (d, JP,C ϭ 17.5 Hz, P-CH(Ph)), 1.68Ϫ1.70 (m, 6 H, Cp*-CH3), 1.92 (s, 3 H, Cp*-CH3), 1.98 (s, 3 H,
1
63.0 (d, JP,C ϭ 10.0 Hz, Cp*-C1), 125.0 (d, JP,C ϭ 2.9 Hz, Ph),
127.2 (d, JP,C ϭ 2.3 Hz, Ph), 127.5 (d, JP,C ϭ 2.3 Hz, Ph), 131.6 (d,
JP,C ϭ 7.4 Hz, Cp*), 134.0 (s, Ph), 136.8 (d, JP,C ϭ 1.6 Hz, Cp*),
Cp*-CH3), 3.34 (s, 3 H, Ar-OCH3), 4.46 (d, JP,H ϭ 2.0 Hz, 3 H,
POC-H), 6.46 (d, JH,H ϭ 8.2 Hz, 1 H, Ar), 6.88 (ЉtЉ, JH,H ϭ 7.4 Hz,
1 H, Ar), 7.09 (ЉtЉ, JH,H ϭ 7.9 Hz, 1 H, Ar), 7.60 (dЉqЉ, JH,H
ϭ
140.7 (d, JP,C ϭ 6.1 Hz, Cp*), 143.0 (d, JP,C ϭ 7.8 Hz, Cp*), 194.8 7.5 Hz (d), JH,H
ϭ
0.7 Hz (q), 1 H, Ar); 13C{1H} NMR
2
1
2
(d, JP,C ϭ 8.4, JW, C ϭ 125.2 Hz, cis-CO), 197.3 (d, JP,C
37.5 Hz, trans-CO); 31P{1H} NMR: δ ϭ 31.6 (sSat 1JW, P
309.0 Hz). MS: m/z (%)
[{(OC)5WPCp*}·ϩ], 456 (26) [(M-5CO)·ϩ], 406 (100)
ϭ
(125.8 MHz, 25 C, C6D6): δ ϭ 10.5 (d, JP,C ϭ 3.0 Hz, Cp*-CH3),
11.6 (d, JP,C ϭ 2.0 Hz, Cp*-CH3), 11.6 (s, Cp*-CH3), 12.1 (s, Cp*-
CH3), 13.3 (d, JP,C ϭ 5.0 Hz, Cp*-C1-CH3), 54.7 (d, JP,C ϭ 20.2 Hz,
POCH), 54.8 (s, Ar-OCH3), 64.3 (d, JP,C ϭ 10.0 Hz, Cp*-C1), 110.0
,
ϭ
ϭ
596 (17) [M·ϩ], 490 (57)
[{(OC)2WPCp*}·ϩ], 378 (22) [{(OC)WPCp*}·ϩ], 327 (13) (d, JP,C ϭ 2.0 Hz, m-Ar-H), 121.0 (d, JP,C ϭ 2.0 Hz, m-Ar-H), 124.1
[{(OC)4WP}·ϩ], 299 (14) [{(OC)3WP}·ϩ], 271 (5) [{(OC)2WP}·ϩ],
(s, i-Ar), 127.3 (d, JP,C ϭ 4.0 Hz, o-Ar-H), 129.5 (d, JP,C ϭ 2.0 Hz,
135 (22) [(Cp*)·ϩ], 119 (18) [(Cp*-Me-H)·ϩ], 105 (9) p-Ar-H), 133.6 (d, JP,C ϭ 7.0 Hz, Cp*), 138.2 (s, Cp*), 141.9 (d,
[(Cp*-2Me)·ϩ], 91 (5) [(Cp*-2Me-CH2)·ϩ]. IR (KBr; ν˜(CO)): ν˜ ϭ JP,C ϭ 6.0 Hz, Cp*), 144.1 (d, JP,C ϭ 8.0 Hz, Cp*), 157.9 (s, o-Ar-
1937 (m), 1992 (s), 2074 (s) cmϪ1; X-ray crystallographic analysis:
OCH3), 194.4 (d, JP,C ϭ 8.0 Hz, cis-CO), 195.9 (d, JP,C ϭ 36.9 Hz,
structure has been deposited at the Cambridge Crystallographic trans-CO); 31P{1H} NMR (202.4 MHz, 25 °C, C6D6): δ ϭ 30.9
1
Data Centre under the number CCDC-647516.
(sSat, JW, P ϭ 306.4 Hz). MS: m/z (%) ϭ 626 (17) [M·ϩ], 542 (14)
1168 www.zaac.wiley-vch.de
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2009, 1163Ϫ1171

Facile Synthesis of Pentacarbonyltungsten(0) Complexes
2
[(M-3CO)·ϩ], 135 (100) [(Cp*)·ϩ], 119 (32) [(Cp*-Me-H)·ϩ], 105 Cp*), 193.6 (dSat, 1JW, C ϭ 125.4, JP,C ϭ 8.4 Hz, cis-CO), 194.9 (d,
1
(19) [(Cp*-2Me)·ϩ], 91 (27) [(Cp*Ϫ2MeϪCH2)·ϩ]. IR (KBr;
2JP,C ϭ 35.6 Hz, trans-CO); 31P{1H} NMR: δ ϭ 22.8 (sSat, JW, P
ϭ
ν˜(CO)): ν˜ ϭ 1935 (m/s), 1989 (m/s), 2078 (s) cmϪ1
.
298.8 Hz). MS: m/z (%) ϭ 562 (10) [M·ϩ], 490 (39) [{(OC)5WPCp*
·ϩ], 406 (100) [{(OC)2WPCp*}·ϩ], 378 (20) [{(OC)WPCp*}·ϩ],
}
[{Me5C5P
T
CH(tBu)؊O
}W(CO)5] (7d): Yield: 418 mg (86 %) (B); 327 (11) [{(OC)4WP}·ϩ], 299 (11) [{(OC)3WP}·ϩ], 271 (6)
U
m.p. 104 °C; C20H25O6PW (576.22 g·molϪ1): calc: C 41.69, H [{(OC)2WP}·ϩ], 135 (30) [(Cp*)·ϩ], 119 (14) [(Cp*-Me-H)·ϩ], 105
4.37 %; exp: C 41.76, H 4.39 %. 1H NMR: δ ϭ 0.74 (d, JP,H
ϭ
(10) [(Cp*-2Me)·ϩ], 91 (4) [(Cp*-2Me-CH2)·ϩ]. IR (KBr; ν˜(CO)):
3
10.4 Hz, 3 H, Cp*-C1-CH3), 1.08 (s, 9 H, tBu-CH3), 1.61Ϫ1.64 (mc, ν˜ ϭ 1923 (s), 1939 (s), 1965 (s), 1994 (m), 2075 (m) cmϪ1
.
9 H, Cp*-CH3), 1.88 (s, 3 H, Cp*-CH3), 2.92 (s, 1 H, POC-H);
13C{1H} NMR: δ ϭ 9.3 (d, JP,C ϭ 3.2 Hz, Cp*-CH3), 10.0 (d, JP,C ϭ
1.3 Hz, Cp*-CH3), 10.5 (d, JP,C ϭ 2.3 Hz, Cp*-CH3), 10.7 (d,
JP,C ϭ 1.0 Hz, Cp*-CH3), 13.1 (d, JP,C ϭ 4.8 Hz, Cp*-C1-CH3),
26.6 (d, JP,C ϭ 3.6 Hz, tBu-CH3 (3 ϫ)), 31.1 (s, tBu), 62.6 (d, JP,C ϭ
[{Me5C5P
T
CH(Me)؊O}W(CO)5] (7g): Yield 112 mg (51 %) (A) or
U
240 mg (98 %) (B); m.p. 108 °C; C17H19O6PW (534.14 g·molϪ1):
1
calc: C 38.23 %, H 3.59 %; exp: C 38.01, H 3.66 %. H NMR: δ ϭ
0.70 (d, 3JP,H ϭ 11.3 Hz, 3 H, Cp*-C1-CH3), 1.28 (dd, 3JP,H ϭ 14.2,
3JH,H ϭ 5.9 Hz, 3 H, POC-CH3), 1.55 (s, 3 H, Cp*-CH3), 1.63 (mc,
3 H, Cp*-CH3), 1.65 (mc, 3 H, Cp*-CH3), 1.86 (mc, 3 H, Cp*-
7.4 Hz, Cp*-C1), 63.0 (d, JP,C ϭ 19.1 Hz, POCH), 132.6 (d, JP,C
ϭ
8.1 Hz, Cp*), 138.4 (d, JP,C ϭ 2.6 Hz, Cp*), 140.1 (d, JP,C ϭ 6.1 Hz,
Cp*), 142.5 (d, JP,C ϭ 7.4 Hz, Cp*), 194.2 (dSat, JP,C ϭ 8.1, JW, C ϭ
125.8 Hz, cis-CO), 194.5 (d, JP,C ϭ 35.9 Hz, trans-CO); 31P{1H}
CH3), 2.94 (q, JP,H ϭ 0.6, JH,H ϭ 5.9 Hz, 1 H, POC-H); 13C{1H}
3
NMR: δ ϭ 9.3 (d, JP,C ϭ 2.9 Hz, Cp*-CH3), 10.0 (d, JP,C ϭ 1.6 Hz,
NMR: δ ϭ 11.0 (sSat,
1JW, P ϭ 298.8 Hz). MS: m/z (%) ϭ 576 (7)
Cp*-CH3), 10.1 (d, JP,C ϭ 2.3 Hz, Cp*-CH3), 10.6 (d, JP,C
ϭ
1.6 Hz, Cp*-CH3), 11.7 (d, JP,C ϭ 4.8 Hz, Cp*-C1-CH3), 15.4 (d,
JP,C ϭ 2.9 Hz, POC-CH3), 51.2 (d, JP,C ϭ 22.0 Hz, POCH), 61.8
(d, JP,C ϭ 7.8 Hz, Cp*-C1), 131.9 (d, JP,C ϭ 7.1 Hz, Cp*), 137.1 (d,
[M·ϩ], 490 (42) [{(OC)5WPCp*}·ϩ], 406 (100) [{(OC)2WPCp*}·ϩ],
378 (19) [{(OC)WPCp*}·ϩ], 327 (11) [{(OC)4WP}·ϩ], 299 (13)
[{(OC)3WP}·ϩ], 271 (6) [{(OC)2WP}·ϩ], 166 (7) [(PCp*)·ϩ], 135
(30) [(Cp*)·ϩ], 119 (15) [(Cp*-Me-H)·ϩ], 105 (11) [(Cp*-2Me)·ϩ],
91 (5) [(Cp*-2Me-CH2)·ϩ]. IR (KBr; ν˜(CO)): ν˜ ϭ 1921 (s), 1947
J
P,C ϭ 1.9 Hz, Cp*), 140.2 (d, JP,C ϭ 5.8 Hz, Cp*), 142.7 (d, JP,C ϭ
2
1
7.8 Hz, Cp*), 193.5 (dSat, JP,C ϭ 8.7, JW, C ϭ 125.3 Hz, cis-CO),
195.0 (d, JP,C ϭ 35.6 Hz, trans-CO); 31P{1H} NMR: δ ϭ 23.0
2
(s), 1991 (m), 2074 (m) cmϪ1
.
1
(sSat, JW, P ϭ 297.5 Hz). MS: m/z (%) ϭ 534 (15) [M·ϩ], 490 (48)
[{(OC)5WPCp*}·ϩ], 406 (100) [{(OC)2WPCp*}·ϩ], 378 (33)
[{(OC)WPCp*}·ϩ], 327 (18) [{(OC)4WP}·ϩ], 299 (16)
[{(OC)3WP}·ϩ], 271 (9) [{(OC)2WP}·ϩ], 135 (23) [(Cp*)·ϩ], 119
(18) [(Cp*-Me-H)·ϩ], 105 (14) [(Cp*-2Me)·ϩ], 91 (6) [(Cp*-2Me-
[{Me5C5P
T
CH(iPr)؊O}W(CO)5] (7e): Yield: 102 mg (44 %) (A);
U
m.p. 118 °C; C19H23O6PW (562.20 g·molϪ1): calc: C 40.59, H
4.12 %; exp: C 40.45, H 4.27 %. 1H NMR: δ ϭ 0.75 (d, JP,H
ϭ
3
11.3 Hz, 3 H, Cp*-C1-CH3), 0.95 (d, JH,H ϭ 6.6 Hz, 3 H, iPr-
3
CH2)·ϩ]. IR (KBr; ν˜(CO)): ν˜ ϭ 1931 (m), 1990 (s), 2076 (s) cmϪ1
.
3
3
CH3), 1.09 (dd, JP,H ϭ 1.2, JH,H ϭ 6.6 Hz, 3 H, iPr-CH3), 1.62
(s, 3 H, Cp*-CH3), 1.64 (mc, 3 H, Cp*-CH3), 1.66 (mc, 3 H,
Cp*ϪCH3), 1.68-1.82 (m, 1 H, POCϪCH), 1.88 (s, 3 H, Cp*-CH3),
3
2.71 (d, JPH ϭ 10.1 Hz, 1 H, POC-H); 13C{1H} NMR: δ ϭ 9.2 (d,
General Procedure for the Preparation of Complexes
JP,C ϭ 3.2 Hz, Cp*-CH3), 10.0 (d, JP,C ϭ 1.3 Hz, Cp*-CH3), 10.2
(d, JP,C ϭ 1.9 Hz, Cp*-CH3), 10.6 (d, JP,C ϭ 1.6 Hz, Cp*-CH3),
12.0 (d, JP,C ϭ 5.2 Hz, Cp*-C1-CH3), 17.9 (s, iPr-CH3(1)), 18.1 (d,
[{(Me3Si)2HCPT U}W(CO)5] (8a؊f)
CH(R2)؊O
To
a solution of [{(Me3Si)2HCPCl2}W(CO)5] (2) (200 mg,
J
P,C ϭ 10.0 Hz, iPr-CH3(2)), 28.9 (d, JP,C ϭ 3.2 Hz, POC-CH), 60.7
0.31 mmol) and 12-crown-4 (0.31 mmol) in diethyl ether (10 mL),
a tert-butyllithium solution (0.2 mL, 0.31 mmol, 1.6 m) was added
dropwise at Ϫ80 °C while stirring. The mixture was stirred for five
minutes at this temperature and afterwards the corresponding alde-
hyde (0.31 mmol) was added. The solution was stirred for ad-
ditional 90 min while gently warming to 0 °C and then warmed up
to ambient temperature. The solvents were then removed in vacuo
(ca. 0.01 bar) and the residue was extracted with n-pentane
(20 mL). The products were purified by column chromatography
(Al2O3, Ϫ30 °C, petroleum ether.
(d, JP,C ϭ 20.0 Hz, POC-H), 61.9 (d, JP,C ϭ 8.1 Hz, Cp*-C1), 131.7
(d, JP,C ϭ 7.1 Hz, Cp*), 137.3 (d, JP,C ϭ 1.9 Hz, Cp*), 140.2 (d,
JP,C ϭ 6.1 Hz, Cp*), 142.9 (d, JP,C ϭ 7.8 Hz, Cp*), 193.5 (dSat
,
1JW, C ϭ 125.4, JP,C ϭ 8.4 Hz, cis-CO), 194.9 (d, JP,C ϭ 35.6 Hz,
2
2
trans-CO); 31P{1H} NMR: δ ϭ 24.7 (sSat, JW, P ϭ 298.8 Hz). MS:
1
m/z (%) ϭ 562 (17) [M·ϩ], 490 (34) [{(OC)5WPCp*}·ϩ], 406 (100)
[{(OC)2WPCp*}·ϩ], 378 (21) [{(OC)WPCp*}·ϩ], 327 (11)
[{(OC)4WP}·ϩ], 299 (14) [{(OC)3WP}·ϩ], 271 (7) [{(OC)2WP}·ϩ],
135 (22) [(Cp*)·ϩ], 119 (16) [(Cp*-Me-H)·ϩ], 105 (13)
[(Cp*-2Me)·ϩ], 91 (5) [(Cp*-2Me-CH2)·ϩ]. IR (KBr; ν˜(CO)): ν˜ ϭ
1934 (m), 2077 (s) cmϪ1
.
[{(Me3Si)2HCP
T
CH(Ph)؊O}W(CO)5] (8a): Yield 127.4 mg (60 %);
U
m.p. 96 °C. C19H25O6PSi2W (620.04 g·molϪ1): calc: C 36.78, H
4.06 %; exp: C 36.99, H 4.36 %. 1H NMR: δ ϭ 0.30 (s, 9 H,
[{Me5C5PCH(nPr)؊O}W(CO)5] (7f): Yield: 171 mg (72 %) (B);
T
U
m.p. 62 °C; C19H23O6PW (562.20 g·molϪ1): calc: C 40.59, H Si(CH3)3), 0.39 (s, 9 H, Si(CH3)3), 1.28 (s, 1 H, CH(Si(CH3)3)2),
4.12 %; exp: C 41.26, H 4.48 %. 1H NMR: δ ϭ 0.75 (d, JP,H
ϭ
4.40 (d, 1 H, JP,H ϭ 1.9 Hz, PhC(H)O), 7.10 (mc, 3 H, Ph), 7.36
3
2
11.4 Hz, 3 H, Cp*-C1-CH3), 0.90 (t, JH,H
ϭ
7.3 Hz, 3 H, (mc, 2 H, Ph); 13C{1H} NMR: δ ϭ Ϫ0.4 (d, JP,C ϭ 4.2 Hz,
3
3
3
1
nPr-CH3), 1.36Ϫ1.48 (m, 2 H, nPr-CH2), 1.61Ϫ1.72 (m, 11 H, 3 ϫ
Cp*-CH3 and nPr-CH2), 1.88 (s, 3 H, Cp*-CH3), 3.00 (t, JH,H
Si(CH3)3), 0.0 (d, JP,C ϭ 2.2 Hz, Si(CH3)3), 30.5 (d, JP,C ϭ
ϭ
18.8 Hz, CH(Si(CH3)3)2), 57.9 (d, 1JP,C ϭ 27.5 Hz, PC(H)O), 123.5
6.7 Hz, 1 H, POC-H); 13C{1H} NMR: δ ϭ 9.3 (d, JP,C ϭ 3.2 Hz, (d, JP,C ϭ 3.2 Hz, Ph), 126.1 (d, J ϭ 2.9 Hz, Ph), 126.7 (d, J ϭ
3
Cp*-CH3), 10.0 (d, JP,C ϭ 1.6 Hz, Cp*-CH3), 10.1 (d, JP,C
ϭ
2.3 Hz, Ph), 133.3 (s, p-Ph), 192.7 (d, 2JP,C ϭ 8.4 Hz, cis-CO); 194.9
2
2.3 Hz, Cp*-CH3), 10.6 (d, JP,C ϭ 1.9 Hz, Cp*-CH3), 11.9 (d, (d, JP,C
ϭ δ ϭ 38.2
35.6 Hz, trans-CO); 31P{1H} NMR:
JP,C ϭ 5.2 Hz, Cp*-C1-CH3), 12.5 (s, POC(H)CH2CH2-CH3), 18.9 (ssat, JW, P ϭ 307.7 Hz). MS: m/z (%) ϭ 620 (20) [M·ϩ], 514 (15)
1
(d, JP,C ϭ 4.8 Hz, POC(H)CH2-CH2), 31.7 (d, JP,C ϭ 2.6 Hz,
[(M-Ph(H)CO)·ϩ], 486 (15) [(M-Ph(H)CO-CO)·ϩ], 428 (50)
[(M-PhC(H)O-3CO)·ϩ], 400 (60) [(M-Ph(H)CO-4CO)·ϩ]; 86 (100)
[CH(Si(CH3)3)2·ϩ]. IR (KBr; ν˜(CO)): ν˜ ϭ 1880 (s), 1924 (m), 2077
POC(H)-CH2), 55.2 (d, JP,C ϭ 20.7 Hz, POCH), 61.8 (d, JP,C
ϭ
7.8 Hz, Cp*-C1), 131.8 (d, JP,C ϭ 7.1 Hz, Cp*), 137.2 (d, JP,C
ϭ
1.6 Hz, Cp*), 140.2 (d, JP,C ϭ 6.1 Hz, Cp*), 142.7 (d, JP,C ϭ 7.8 Hz, (s), 2067(s) cmϪ1
.
Z. Anorg. Allg. Chem. 2009, 1163Ϫ1171
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
1169

´
R. Streubel, M. Bode, J. Marinas Perez, G. Schnakenburg, J. Daniels, M. Nieger, P. G. Jones
ARTICLE
[{(Me3Si)2HCP
T
CH(o-Tol)؊O
U
}W(CO)5] (8b): Yield 130.2 mg
[{(Me3Si)2HCP
T
CH(nPr)؊O}W(CO)5] (8f): Yield 110.1 mg (55 %);
U
(60 %); m.p. 65 °C. C20H27O6PSi2W (634.04 g·molϪ1): calc: C m.p. 68 °C; C16H27O6PSi2W (586.37 g·molϪ1): calc: C 32.77, H
37.86, H 4.29 %; exp: C 38.12, H 4.57 %. 1H NMR: δ ϭ 0.16 (s, 4.64 %; exp: C 32.20, H 4.56 %. 1H NMR: δ ϭ 0.25 (s, 9 H,
9 H, Si(CH3)3), 0.22 (s, 9 H, Si(CH3)3), 1.14 (s, 1 H,
2
Si(CH3)3), 0.29 (s, 9 H, Si(CH3)3), 1.05 (t, 3 H, JH,H ϭ 6.5, CH3),
CH(Si(CH3)3)2), 2.33 (s, 3 H, o-CH3), 4.26 (s, 1 H, PhC(H)O), 7.00 1.15 (s, 1 H, CH(Si(CH3)3)2), 1.6 (m, 2 H, CH2), 1.8 (m, 2 H, CH2),
2
(m, 4 H, Ph); 13C{1H} NMR: δ ϭ 1.6 (d, 3JP,C ϭ 3.14 Hz, Si(CH3)3),
3.1 (t, 1 H, JP,H ϭ 9 Hz, PC(H)O); 13C{1H} NMR: δ ϭ Ϫ0.6 (d,
3
1
1.8 (d, JP,C ϭ 2.3 Hz, Si(CH3)3), 32.7 (d, JP,C ϭ 20.3 Hz,
3JP,C ϭ 4.5 Hz, Si(CH3)3), 0.0 (d, 3JP,C ϭ 2.2 Hz, Si(CH3)3), 11.9 (s,
CH2CH3), 17.8 (d, JP,C ϭ 6.1 Hz, CH2), 28.5 (d, JP,C ϭ 16.4 Hz,
CH(Si(CH3)3)2), 31.4 (d, JP,C ϭ 30.7 Hz, CH2), 57.4 (d, JP,C ϭ
1
2
3
CH(Si(CH3)3)2), 57.9 (d, JP,C ϭ 24.5 Hz, PC(H)O), 125.6 (d,
3JP,C ϭ 2.1 Hz, Ar), 125.7 (d, JP,C ϭ 4.4 Hz, Ar), 127.6 (d, JP,C
ϭ
3
1
2
2.6 Hz, Ar), 129.7 (d, JP,C ϭ 2.3 Hz, Ar), 128.0 (s, Ar), 131.3 (s, 30.7 Hz, PC(H)O), 193.5 (d, JP,C ϭ 8.4 Hz, cis-CO), 195 (d,
2
2
1
Ar), 193.9 (d, JP,C ϭ 8.4 Hz, cis-CO), 195.1 (d, JP,C ϭ 34.9 Hz,
2JP,C ϭ 33.6 Hz, trans-CO); 31P{1H} NMR: δ ϭ 27.7 (ssat, JW, P
ϭ
trans-CO); 31P{1H} NMR: δ ϭ 41.0 (ssat, JW, P ϭ 306.6 Hz). MS: 302.6 Hz). MS: m/z (%) ϭ 586 (20) [M·ϩ], 543 (27) [M-nPr·ϩ], 514
1
m/z (%) ϭ 634(10) [M·ϩ], 514 (40) [M-Ar-C(H)O·ϩ], 486 (100) (35) [M-nPr-C(H)O·ϩ], 486 (100) [M-nPr-C(H)O-CO·ϩ]; IR (KBr;
[M-Ar-C(H)O-CO·ϩ]. IR (KBr; ν˜(CO)): ν˜ ϭ 1923 (w), 1993 (s), ν˜(CO)): ν˜ ϭ 1930 (m), 1986 (s), 2076 (s) cmϪ1
.
2075 (s), 2957 (s) cmϪ1
.
[{(Me3Si)2HCP
T
CH(o-Anis)؊O}W(CO)5] (8c): Yield 142.5 mg
U
Acknowledgement
(64 %); m.p. 99 °C. C20H27O7PSi2W (650.41 g·molϪ1): calc: C
36.93, H 4.18 %; exp: C 37.30, H 4.42 %. 1H NMR: δ ϭ 0.22 (s,
9 H, Si(CH3)3), 0.30 (s, 9 H, Si(CH3)3), 1.16 (s, 1 H, CH(SiCH3)2),
3.79 (s, 3 H, OCH3), 4.46 (s, 1 H, ArC(H)O), 6.79 (m, 3 H, Ar),
Financial support by ThermPhos International is gratefully
acknowledged.
6.79 (m, 1 H, Ar). 13C{1H} NMR: δ ϭ Ϫ0.8 (d, JP,C ϭ 4.2 Hz,
Si(CH3)3), 0.0 (d, JP,C ϭ 2.2 Hz, Si(CH3)3), 30.4 (d, JP,C
20.2 Hz, CH(Si(CH3)3)2), 52.6 (s, OCH3), 54.7 (d, JP,C ϭ 28.2 Hz,
PC(H)O), 107.3 (d, JP,C ϭ 2.2 Hz, Ar), 118.3 (d, JP,C ϭ 2.4 Hz,
3
3
1
References
ϭ
1
[1] G. V. Röschenthaler, K. Sauerbrey, R. Schmutzler, Chem. Ber.
1978, 111, 3105.
[2] P. A. Bartlett, N. I. Carruthers, B. M. Winter, K. P. Long, J.
Org. Chem. 1982, 47, 1284.
[3] M. T. Boisdon, J. Barrans, J. Chem. Soc., Chem. Commun.
1988, 615.
[4] a) H. Ikeda, S. Inagaki, J. Phys. Chem. A 2001, 105, 10711; b)
D. B. Chesnut, L. D. Quin, Tetrahedron 2005, 61, 12343; c) L.
I. Savostina, R. M. Aminova, V. F. Mironov, Russ. J. General.
Chem. 2006, 76, 1031.
3
Ar), 121.7 (s, Ar), 124.3 (d, JP,C ϭ 4.4 Hz, Ar), 126.8 (d, JP,C
ϭ
2
2.6 Hz, Ar), 155.2 (d, JP,C ϭ 2.6 Hz, Ar), 192.9 (d, JP,C ϭ 8.4 Hz,
cis-CO), 195.2 (d, JP,C ϭ 34.7 Hz, trans-CO); 31P{1H} NMR: δ ϭ
2
1
39.2 (ssat, JW, P ϭ 305.5 Hz). MS: m/z (%) ϭ 650 (60) [M·ϩ], 566
(40) [M-3CO·ϩ], 514 (15) [M-Ar-C(H)O·ϩ], 73 (100) [Si(CH3)3·ϩ].
[{(Me3Si)2HCP
T
(tBu)؊O}W(CO)5] (8d): Yield 100.4 mg (50 %);
U
m.p. 94 °C. C17H29O6PSi2W (600.39 g·molϪ1): calc: C 34.01, H
4.87 %; exp: C 33.88, H 4.86 %. 1H NMR: δ ϭ 0.24 (s, 9 H,
Si(CH3)3), 0.31 (s, 9 H, Si(CH3)3), 1.1 (s, 9 H, (CH3)3), 1.25 (s, 1 H,
CH(Si(CH3)3)2), 2.7 (s, PC(H)O); 13C{1H} NMR: δ ϭ 0.7 (d,
[5] M. Schnebel, I. Weidner, R. Wartchow, H. Butenschön, Eur. J.
Org. Chem. 2003, 4363.
[6] S. Bauer, A. Marinetti, L. Ricard, F. Mathey, Angew. Chem.
1990, 102, 1188; Angew. Chem. Int. Ed. Engl. 1990, 29, 1166.
[7] O. Krahe, F. Neese, R. Streubel, Chem. Eur. J. 2009, 15, 2594.
[8] W. W. Schoeller in Multiple Bonds and Low Coordination in
Phosphorus Chemistry (Eds.: M. Regitz, O. J. Scherer), Georg
Thieme Verlag, Stuttgart, 1990, p. 1.
[9] R. Streubel, A. Kusenberg, J. Jeske, P. G. Jones, Angew. Chem.
1994, 106, 2564; Angew. Chem. Int. Ed. Engl. 1994, 33, 2427.
[10] R. Streubel, A. Ostrowski, H. Wilkens, F. Ruthe, J. Jeske, P. G.
Jones, Angew. Chem. 1997, 109, 409; Angew. Chem. Int. Ed.
Engl. 1997, 36, 378.
3JP,C ϭ 4.5 Hz, Si(CH3)3), 1.5 (d, JP,C ϭ 2.3 Hz, Si(CH3)3), 24.5
3
2
2
(d, JP,C ϭ 4 Hz, CH3) 27.3 (d, JP,C ϭ 4 Hz, 2CH3), 31.0 (s,
2
C(CH3)3), 33.6 (d, JP,C ϭ 15.4 Hz, CH(Si(CH3)3)2), 67.1 (d,
1JP,C ϭ 28.49 Hz, PC(H)O), 195.5 (d, 2JP,C ϭ 8.4 Hz, cis-CO), 196.5
2
(d, JP,C
ϭ δ ϭ 22.5
33.6 Hz, trans-CO); 31P{1H} NMR:
1
(ssat, JW, P ϭ 298.8 Hz). MS: m/z (%) ϭ 600 (13) [M·ϩ], 557 (30)
[M-CO-O·ϩ], 527 (20) [M-CO-O·ϩ], 514 (40) [M-tBu-C(H)O·ϩ],
486 (100) [M-tBu-C(H)O-CO·ϩ]. IR (KBr; ν˜(CO)): ν˜ ϭ 1934 (m),
[11] A. Özbolat, G. von Frantzius, M. Nieger, R. Streubel, Angew.
Chem. 2007, 119, 9488; Angew. Chem. Int. Ed. 2007, 46, 9327.
[12] M. Bode, P. G. Jones, G. Schnakenburg, R. Streubel, Or-
ganometallics 2008, 27, 2664.
1986(s), 2076 (s) cmϪ1
.
[{(Me3Si)2HCP
T
CH(iPr)؊O}W(CO)5] (8e): Yield 106.3 mg (53 %);
U
´
[13] H. Helten, J. M. Perez, J. Daniels, R. Streubel, Organometallics
m.p. 86 °C. C16H27O6PSi2W (586.37 g·molϪ1): calc: C 32.77, H
4.64 %; exp: C 32.68, H 4.65 %. 1H NMR: δ ϭ 0.25 (s, 9 H,
Si(CH3)3), 0.30 (s, 9 H, Si(CH3)3), 1.05 (m, 1 H, CH(Si(CH3)3)2),
2009, 28, 1221.
[14] 1 was synthesized according to: P. Jutzi, H. Saleske, D. Nadler,
J. Organomet. Chem. 1976, 118, C8.
2
2
1.17 (d, 3 H, JH,H ϭ 6.5 Hz, CH3), 1.21 (d, 3 H, JH,H ϭ 6.7 Hz,
[15] A. A. Khan, C. Wismach, P. G. Jones, R. Streubel, Dalton
Trans. 2003, 12, 2483.
2
CH3), 1.60 (m, 1 H, CH(CH3)2), 2.75 (d, 1 H, JP,H ϭ 9.82 Hz,
PC(H)O); 13C{1H} NMR: δ ϭ Ϫ0.4 (d, JP,C ϭ 4.5 Hz, Si(CH3)3),
3
[16] M. Bode, Universität Bonn, planned Dissertation.
[17] Reactions of complexes 3 with various iodo organic com-
pounds will be described soon: R. Streubel, A. Özbolat-Schön,
M. Bode, L. Duan, G. von Frantzius, J. Daniels, A. Pepiol, P.
3
0.0 (d, JP,C ϭ 2.6 Hz, Si(CH3)3), 17.2 (s, CH(CH3)2), 17.4 (d,
1JP,C ϭ 11.6 Hz, CH(CH3)2), 29.0 (d, CH(CH3)2, JP,C ϭ 3.3 Hz),
3
28.7 (d, CH(Si(CH3)3)2, 3JP,C ϭ 17.1 Hz), 62.9 (d, JP,C ϭ 28.7 Hz,
1
`
Farras Costa, A. Vaca, F. Teixidor, C. Vin˜as Teixidor, manu-
2
2
PC(H)O), 193.4 (d, JP,C ϭ 8.4 Hz, cis-CO), 195 (d, JP,C
ϭ
script in preparation.
33.6 Hz, trans-CO); 31P{1H} NMR: δ ϭ 31.9 (ssat, JW, P ϭ 298.8).
MS: m/z (%) ϭ 586 (15) [M·ϩ], 543 (30) [M-iPr·ϩ], 514 (40)
[M-iPr-C(H)O·ϩ], 486 (100) [M-iPr-C(H)O-CO·ϩ]. IR (KBr;
1
[18] For phosphirane complexes, see: F. Mathey, Chem. Rev. 1990,
90, 997.
[19] For azaphosphiridine complexes, see: a) R. Streubel, A. Os-
trowski, H. Wilkens, F. Ruthe, J. Jeske, P. G. Jones, Angew.
ν˜(CO)): ν˜ ϭ 1930 (m), 1986 (s), 2067(s) cmϪ1
.
1170
www.zaac.wiley-vch.de
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2009, 1163Ϫ1171

Facile Synthesis of Pentacarbonyltungsten(0) Complexes
Chem. 1997, 109, 409; Angew. Chem. Int. Ed. Engl. 1997, 36,
378; b) N. H. Tran Huy, L. Ricard, F. Mathey, Heteroat. Chem.
1998, 9, 597; c) M. J. M. Vlaar, P. Valkier, F. J. J. de-Kanter,
M. Schakel, A. W. Ehlers, A. L. Spek, M. Lutz, K. Lam-
mertsma, Chem. Eur. J. 2001, 7, 3551.
[20] S. Fankel, G. Schnakenburg, R. Streubel, unpublished results.
[21] G. M. Sheldrick, Acta Crystallogr., Sect. A 2008, 64, 112.
Received: January 22, 2009
Published Online: April 16, 2009
Z. Anorg. Allg. Chem. 2009, 1163Ϫ1171
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
1171