Photochemical reactions of W(CO)6 with hydrosilanes: Synthesis, spectroscopic characteristic, and crystal structure of W(CO)3(η 6-PhSiHPh2)

Article abstract of DOI:10.1016/j.jorganchem.2004.08.049

Photolysis of W(CO)₆ in the presence of Ph₃SiH in n-heptane leads to the formation of the first tricarbonyl(η⁶- triphenylhydrosilane)tungsten complex W(CO)₃(η⁶- PhSiHPh₂) (1) in good yield

Full text of DOI:10.1016/j.jorganchem.2004.08.049

Journal of Organometallic Chemistry 690 (2005) 685–690
www.elsevier.com/locate/jorganchem
Photochemical reactions of W(CO)6 with hydrosilanes: synthesis,
spectroscopic characteristic, and crystal structure of
W(CO)3(g6-PhSiHPh2)
*
´
Agnieszka Ga˛dek, Andrzej Kochel, Teresa Szymanska-Buzar
Faculty of Chemistry, University of Wrocław, 14 F. Joliot-Curie Str., 50383 Wrocław, Poland
Received 28 April 2004; accepted 9 August 2004
Abstract
Photolysis of W(CO)6 in the presence of Ph3SiH in n-heptane leads to the formation of the first tricarbonyl(g6-triphenylhydros-
ilane)tungsten complex W(CO)3(g6-PhSiHPh2) (1) in good yield (ca. 70%). The molecular structure of the new tungsten–silane com-
pound was established by single-crystal X-ray diffraction studies and characterized by IR, UV–Vis, 1H, 13C{1H}, and 29Si{1H}
NMR spectroscopy.
ꢀ 2004 Elsevier B.V. All rights reserved.
Keywords: Tungsten; Silicon; X-ray structure; Silane complexes
1. Introduction
which the W(CO)3 moiety is bonded to one or two phe-
nyl rings of Ph3SiH: W(CO)3(g6-PhSiHPh2) (1) and
[W(CO)3(g6-Ph)]2SiHPh (2).
The chemistry of transition metal–silane complexes
has been studied extensively owing to their intermediacy
in catalytic hydrosilylation of olefins, acetylenes or ke-
tones [1]. We have recently found that the photochemi-
cal reaction of W(CO)6 with diphenylsilane, Ph2SiH2,
gave a dinuclear silylene bridged complex, (l-SiPh2)W2-
(CO)10, through an intermediate hydrido-silyl species
[2]. We have now applied this methodology to a much
bulkier silane, Ph3SiH, to detect the product of its reac-
tion with W(CO)6. Here we report that the reaction of
W(CO)6 with Ph3SiH proceeds with retention of the
Si–H bond to afford only g6-arene-type compounds, in
Complexes of the M(CO)3(g6-arene) type have been
intensively studied due to their potential applications
in homogeneous catalysis and organic synthesis [3] and
in construction of molecules with large second-order
optical nonlinearities (NLO materials) [4].
Although there have been several tungsten com-
plexes of the W(CO)3(g6-arene) type [5], there have
been no accounts of the crystal structure of such a
complex with a silyl substituent at the g6-arene ring.
It seemed very interesting to reveal the effect of a
hydrosilane substituent at the g6-aromatic ring on its
structure and reactivity.
In an attempt to reveal whether compound 1 could be
used, we studied the solution properties of the latter
compound by IR, UV–Vis, H, 13C{1H}, and 29Si{1H}
NMR spectroscopy. The solid-state structure of 1 was
established by single-crystal X-ray diffraction studies
(Fig. 1).
1
*
Corresponding author. Tel.: +48 71 375 7221; fax: +48 71 328 23
48.
E-mail address: tsz@wchuwr.chem.uni.wroc.pl (T. Szyman´ska-
Buzar).
0022-328X/$ - see front matter ꢀ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.08.049

686
A. Ga˛dek et al. / Journal of Organometallic Chemistry 690 (2005) 685–690
O
C
O
O
C20
C
C
C27
C23
W
C19
C28
C21
H
H
C
Ph
Ph
hν / -CO
C26
Si
+
Si
C18
W(CO)6 + Ph3SiH
n-heptane
C22
O2
C17
Ph
W
W
C25
C2
O1
C
C
O
O
C
O
O
C
O
C
O
C1
Si
C24
1 (70%)
2 (7%)
W
C3
C11
O3
H1a
Scheme 1. Synthesis of W(CO)3(g6-PhSiHPh2) (1).
C16
C13
C15
C12
À20.71 ppm, respectively. In the IR spectra (KBr) of 1
and 2, the m(Si–H) band appears at 2158 and 2141
cmÀ1, respectively. The m(C„O) bands for 1 are ob-
served at a similar frequency (1983 and 1914 cmÀ1 in
n-heptane) as for the analogous g6-arene complexes [5].
C14
Fig. 1. ORTEP diagram of W(CO)3(g6-PhSiHPh2) (1).
1
In H NMR spectra (CDCl3) of 1, the proton signals
of the g6-phenyl ring are in their expected positions in
the range between 5.5 and 5.1 ppm, while signals of
the uncoordinated phenyl protons lie in the region from
7.6 to 7.4 ppm and are shifted downfield by ca. 0.2 ppm
in comparison with the free ligand. Comparison with the
chemical shift at 5.36 ppm of the unsubstituted benzene
ring in W(CO)3(g6-C6H6) [5e] showed that the presence
of the Ph2SiH group at the g6-phenyl ring allows Hpara
protons to resonate at a higher frequency (dH = 5.57),
while Hortho and Hmeta protons resonate at lower fre-
quencies: dH = 5.34 and 5.19, respectively.
2. Results and discussion
2.1. Synthesis and spectroscopic characteristic of 1
Irradiation (6 h) of a solution of W(CO)6 (1.28 mmol)
and Ph3SiH (1.28 mmol) in n-heptane (80 cm3) with a
200 W high-pressure Hg lamp produced quantitatively
a new carbonyl compound of tungsten, identified due
to two strong bands in the m(C„O) region: 1983 and
1914 cmÀ1. After evaporation of volatiles under vac-
uum, the residue analyzed for carbon content appeared
to be a mixture of compounds containing mainly
W(CO)3(Ph3SiH) (1), possibly contaminated with a
ditungsten complex in which the W(CO)3 moiety is at-
tached to two phenyl rings of Ph3SiH, i.e. [W(CO)3]2Ph3-
SiH (2) (Anal. Found C, 44.37 vs Calcd 47.75 for 1, and
36.21 for 2). Analysis of the crude product by 1H NMR
spectroscopy in CDCl3 solution at room temperature
showed the presence of three different compounds con-
taining the Si–H bond. Those compounds were identi-
fied as uncoordinated Ph3SiH (dH = 5.51, JSi–H = 199
Hz), compound 1 (dH = 5.50, JSi–H = 210 Hz), and the
ditungsten complex 2 (dH = 5.36), approximately in the
ratio 0.3/1/0.1, respectively (Scheme 1).
The isolation of compound 1 from the reaction mix-
ture (ca. 0.4 g, 60% yield) was achieved during the puri-
fication process (washing off Ph3SiH with cold (ca. 0 ꢁC)
n-heptane and crystallization from CH2Cl2/n-heptane at
À20 ꢁC). However, the ditungsten complex 2, was not
isolated in a pure state in this case.
The 13C NMR spectrum (CDCl3) of 1 exhibits four
carbon signals, characteristic for the g6-arene ligand in
the region 97–88 ppm. The assignment of those signals
was possible due to the characteristic Si–C or C–C cou-
pling constants. The lowest-intensity carbon signal at
dC = 89.99 was assigned to carbon ipso (Cipso–Si) due
to the highest Si–C coupling constants (1JSi–C = 67
Hz). The latter signal is at much higher field than in
spectra of analogous compounds in which the g6-arene
ring is substituted by the alkyl group, e.g. at 109.0
ppm in W(CO)3(g6-C6H5Me) [5e] and at 109.7 in
W(CO)3(g6-1,3,5-C6H3Me3) [5c,f]. Another interesting
feature of the carbon ipso signal is the upfield shift upon
the lowering of the temperature, while for other carbon
signals a downfield shift was observed with the lowering
of temperature.
1
1
The NMR spectra of compounds 1 and 2 are very
close together and, as compound 2 was formed in very
low yield, not all signals of that compound were de-
tected and assigned. The better resolved signals are
due to carbonyl ligands, which give two narrow reso-
nances: dC 208.74 for 1 and d 208.29 for 2, with the same
The retention of the Si–H bond in compounds 1 and
2 is indicated by proton signals with chemical shifts and
1
1
the JSi–H coupling constants very close to those of free
value of the tungsten–carbon coupling constant JW-
Ph3SiH. The silane character of the g6-arene ligand in 1
and 2 was also proved by 29Si NMR spectra, which
exhibited characteristic resonances at À16.42 and
C = 185 Hz. An unprecedented high value of the tung-
sten–carbonyl carbon coupling constant evidences
strong back-donation from dp orbitals of the tungsten

A. Ga˛dek et al. / Journal of Organometallic Chemistry 690 (2005) 685–690
687
Table 2
atom to p* orbitals of the CO ligands. This can also cor-
˚
relate with low p acidity of the g6-phenylsilane ligand in
complex 1.
Selected bond lengths (A) and angles (ꢁ) for 1
Atoms
Distance
Atoms
Angle
The g6-phenyl carbons of 2 resonate in a similar re-
gion as for 1 (98–88 ppm), giving seven signals. Only
Cipso carbons of both g6-phenyl rings resonate at the
same frequency with characteristic high-field shift (from
87.17 ppm at 293 K to 86.89 ppm at 248 K), while for
others carbon signals the downfield shift with lowering
the temperature were observed.
W–C(2)
W–C(1)
W–C(3)
1.969(3)
1.975(3)
1.980(4)
2.324(3)
2.347(3)
2.352(3)
2.359(3)
2.377(3)
2.377(3)
1.874(4)
1.874(3)
1.881(4)
1.44(3)
C(2)–W–C(1)
C(2)–W–C(3)
C(1)–W–C(3)
89.07(13)
89.70(14)
85.50(13)
106.94(13)
102.44(12)
161.49(13)
73.89(19)
74.32(18)
71.17(18)
72.12(18)
73.57(18)
72.67(18)
71.47(18)
71.59(19)
130.95(16)
112.60(15)
111.78(15)
109.52(15)
105.4(13)
109.3(13)
108.0(13)
W–C(12)
W–C(16)
W–C(14)
W–C(13)
W–C(15)
W–C(11)
Si–C(17)
C(2)–W–C(11)
C(1)–W–C(11)
C(3)–W–C(11)
C(13)–C(12)–W
C(11)–C(12)–W
C(12)–C(13)–W
C(14)–C(13)–W
C(15)–C(14)–W
C(13)–C(14)–W
C(16)–C(15)–W
C(14)–C(15)–W
Si–C(11)–W
As might be expected, the electronic spectrum of
compound
1 is rather similar to those of the
Si–C(23)
Si–C(11)
W(CO)3(g6-arene)-type compounds, which show four
absorption bands in the range 220–410 nm [5g,6]. How-
ever, all four bands of 1 are at slightly higher energy and
more intense than those observed for the W(CO)3(g6-
C6Me6) compound [6].
Si–H(1A)
C(11)–C(12)
C(11)–C(16)
C(12)–C(13)
C(13)–C(14)
C(14)–C(15)
C(15)–C(16)
1.432(5)
1.433(5)
1.406(5)
1.425(5)
1.416(5)
1.408(5)
C(17)–Si–C(23)
C(17)–Si–C(11)
C(23)–Si–C(11)
C(17)–Si–H(1A)
C(23)–Si–H(1A)
C(11)–Si–H(1A)
2.2. X-ray crystal structure
The solid-state structure of 1 was determined by X-
ray crystal structure analysis (Table 1, Fig. 1). Selected
bond lengths and angles are listed in Table 2. The struc-
tural parameters of 1 are rather similar to those of
6
˚
and in W(CO)3(g -1,3,5-C6H3Me3) (1.95(2) A) [5b],
˚
while the average W–C(Ph) bond length of 2.356(3) A
in 1 is practically the same as the corresponding average
6
bond lengths in W(CO)3(g -C6H6) (2.365(5) A) [5d] and
in W(CO)3(g -1,3,5-C6H3Me3) (2.35(2) A) [5b]. As
might be expected, the average C–C bond distance of
W(CO)3(g6-C6H6)
[5d]
C6H3Me3) [5b]. The average W–CO bond length of
and
W(CO)3(g6-1,3,5-
˚
6
˚
1.975(3) A in 1 is only slightly longer than the average
˚
6
˚
bond lengths in W(CO)3(g -C6H6) (1.951(6) A) [5d]
6
˚
1.420(5) A in g -phenyl ring of 1 is a slightly longer than
˚
the average C–C bond distance of 1.392(5) A, found for
Table 1
Crystal data and structure refinement parameters for 1
the phenyl rings uncoordinated to the tungsten atom in
1. A projection of the g6-phenyl ring plane onto the trig-
onal plane defined by the three CO ligands in Fig. 2 re-
veals that the W–CO bonds are close to eclipsing the
ring carbon atoms. The least-square plane of the g6-phe-
Empirical formula
Formula weight
Crystal size (mm)
Crystal system
C21H16O3SiW
528.27
0.30 · 0.10 · 0.10
Monoclinic
P1/c (No. 14)
Space group
Unit cell dimensions
˚
nyl ring (rms deviation of fitted atoms = 0.0101 A) is al-
most parallel (a deviation angle of 1.22(5)ꢁ) to the plane
containing the three carbonyl groups. The distance be-
tween the tungsten atom and the center of gravity of
˚
a (A)
6.578(1)
16.625(3)
17.089(3)
95.02(3)
1861.7(5)
4
˚
b (A)
˚
c (A)
6
˚
b (ꢁ)
the g -ring is 1.880(3) A and relates quite well with
3
˚
V (A )
˚
the corresponding distance of 1.886(2)
W(CO)3(g6-1,3,5-C6H3Me3) [5b].
A
in
Z
Dcalcd (g/cm3)
Diffractometer
Radiation
1.885
Kuma KM4CCD
It seemed interesting to compare the solid-state struc-
tures of free Ph3SiH and Ph3SiH coordinated to the
W(CO)3 moiety. Although the structure of Ph3SiH had
earlier been resolved by X-ray diffraction study at room
temperature [7], we decided to repeat this analysis at a
lower temperature (100 K), the same as for the measure-
ment of 1 [8]. The average Si–C distance in 1 is 1.876(4)
˚
Mo Ka (k = 0.71073 A)
Graphite monochromated
100
Temperature (K)
l (mmÀ1
F (000)
)
6.287
1016
4474/0/240
No. of data/restraints/params
Index ranges
À8 6 h 6 8, À21 6 k 6 21,
À22 6 l 621
23,753
˚
A, which is not significantly longer than in a molecule of
No. of reflns collected
Data collected, h min./max. (ꢁ)
Rint
˚
Ph3SiH (1.872(2) A). The sum of the C–Si–C angles is
3.11/28.48
0.0474
1.156
almost the same in free silane molecules (333.27(7)ꢁ)
and those coordinated to W(CO)3 (333.90(15)ꢁ).
Although it is generally difficult to discuss the Si–H
interactions on the basis of X-ray data, the Si–H
S
Final residuals: R1, wR2 (I > 2r(I))
R1, wR2 (all data)
0.0262, 0.0518
0.0347, 0.0539
0.944/À1.000
À3
˚
Dqmax/Dqmin (e A
)
˚
distance of 1.44(3) A in 1 is a little longer than the

688
A. Ga˛dek et al. / Journal of Organometallic Chemistry 690 (2005) 685–690
O1
C12
C23
C13
C1
O3
C3
W
C11
Si
C14
C16
C15
C17
C2
O2
Fig. 2. A projection of the g6-phenyl ring plane onto the trigonal base defined by the three CO ligands in 1.
1
˚
Si–H distance of 1.41(2) A, detected for Ph3SiH mole-
cules in our low-temperature X-ray analysis [8].
In conclusion, during the photochemical reaction of
W(CO)6 and Ph3SiH the Si–H bond is saved and no oxi-
dative addition reaction is observed.
chemical shifts for H NMR spectra were referenced to
the residual protons in CDCl3 at d 7.24. 13C NMR spec-
tra were calibrated to the natural abundance of 13C in
CDCl3 at d 77.00. 29Si NMR shifts were referenced to
SiMe4. The photolysis source was an HBO 200W high-
pressure Hg lamp. Elemental analyses were performed
by the Analytical Laboratory, Faculty of Chemistry,
University of Wrocław, with a Perkin–Elmer 2400
CHN instrument.
Further efforts to explore the photochemical reaction
of W(CO)6 with hydrosilanes in catalytic hydrosilylation
of C@O or C@C bonds are currently in progress.
3. Experimental
3.2. Synthesis of 1
3.1. General information
A solution of W(CO)6 (0.45 g, 1.28 mmol) and
Ph3SiH (0.33 g, 1.27 mmol) in freshly distilled n-heptane
(80 cm3) was irradiated through quartz at room temper-
ature. The course of the reaction was monitored by IR
measurements in solution, and photolysis was stopped
when the IR band of the new compound at 1914 cmÀ1
reached its maximum intensity (ca. 6 h). The volatile
materials were then stripped off the reaction mixture un-
der reduced pressure at room temperature. The residue
(0.63 g) analyzed by IR (in KBr pellets), by NMR
spectroscopy, and for carbon content appeared to con-
sist mainly of complex 1 contaminated with the ditung-
sten complex 2 and free Ph3SiH. The pure compound 1
was separated from this mixture with about 60% yield
The synthesis and manipulation of all chemicals was
carried out under an atmosphere of nitrogen using the
standard Schlenk technique. Solvents and liquid rea-
gents were pre-dried with CaH2 and vacuum transferred
into small storage flasks prior to use. Other chemicals,
W(CO)6, Ph3SiH, and Ph2SiH2, were obtained from
commercial suppliers and were used as received. IR
spectra were measured with a Nicolet 400 FT–IR instru-
ment. UV–Vis absorption spectra were recorded on a
Hewlett–Packard 8452A rapid scan diode array spec-
trometer. 1H, 13C{1H}, and 29Si{1H} NMR spectra were
recorded with a Bruker AMX 500 MHz instrument. The

A. Ga˛dek et al. / Journal of Organometallic Chemistry 690 (2005) 685–690
689
(0.4 g) by washing off Ph3SiH with several portions of
cold (ca. 0 ꢁC) n-heptane. Isolation of analytically pure
compound 1 typically resulted in substantially lower
yield due to the ready solubility of this compound. Dark
yellow single crystals of 1 for X-ray diffraction study
were grown during a slow crystallization process from
CH2Cl2/n-heptane solution at À20 ꢁC.
atoms were included in the refinement, with anisotropic
displacement parameters. Hydrogen atoms were in-
cluded from geometry of molecules and were not re-
fined. Only the hydrogen atom at the Si atom was
included from Dq maps and refined isotropically. The
data were corrected for absorption [9], min./max.
absorption coefficients 0.282/0.728.
3.3. Spectral data for 1
4. Supplementary material
IR (KBr pellet, cmÀ1): 2158 (s), m(Si–H); 1946 (vs),
1879 (s), 1867 (sh,s), 1859 (sh,s), m(CO); 1429 (w), 1113
(w), 1092 (w), 811 (w), 797 (w), 742 (w) 700 (w), 653
The X-ray crystallographic data for compound 1
have been deposited at the Cambridge Crystallographic
Data Centre with deposition no. CCDC-228072. These
data can be obtained free of charge via www.ccdc.ca-
m.ac.uk/conts/retrieving.html (or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cam-
bridge CB2 1EZ, UK; fax: +44 1123 336 033; e-mail:
deposit@ccdc.cam.ac.uk).
1
(vw), 597 (vw), 496 (w), 484 (vw), 469 (vw); H NMR
(CDCl3, 25 ꢁC): dH 7.68 (dd, JH–H = 7.5 and 1.3 Hz,
4Hortho), 7.51 (t, JH–H = 7.5 Hz, 2Hpara), 7.45 (t, JH–H
=
7.5 Hz, 4Hmeta), 5.57 (t, JH–H = 6.3 Hz, 1Hpara), 5.50 (s,
1JSi–H = 210 Hz, 1Si–H), 5.34 (d, JH–H = 6.3, 2Hortho),
5.19 (t, JH–H = 6.3 Hz, 2Hmeta). 13C{1H} NMR (CDCl3,
25 ꢁC): dC 208.74 (1JC–W = 185 Hz, 3CO), 135.77
(1JC–C = 49 Hz, 4Cortho), 130.91 (1JSi–C = 72 Hz,
1JC–C = 49 Hz, 2Cipso), 130.68 (1JC–C = 53 Hz, 2Cpara),
128.36 (1JC–C = 53 and 49 Hz, 4Cmeta), 96.98
(1JC–C = 49 Hz, 2Cortho), 91.73 (1JC–C = 49 Hz, 1Cpara),
89.99 (1JSi–C = 67 Hz, 1Cipso), 88.08 (1JC–C = 49 Hz,
2Cmeta); 29Si{1H} NMR (CDCl3): dSi À16.42. UV–Vis
(kmax, nm (e · 104, l molÀ1 cmÀ1), n-heptane): 226 (4.8),
266 (1.1), 318 (1.2), 370 (0.1).
Acknowledgements
Support of this work was generously provided by the
Polish State Committee for Scientific Research (KBN
Grant No. 4T09A 19125). We are also grateful to S.
´
Baczynski for the measurement of NMR spectra.
3.4. Spectral data for 2
References
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1983 (s), 1914 (s) m(C„O); H NMR (CDCl3, 25 ꢁC):
dH 7.72 (d, JH–H = 7.5, 2Hortho), ca. 7.5 (1Hpara), ca.
7.4 (2Hmeta), 5.62 (t, JH–H = 6.3 Hz, 1Hpara), 5.36 (s,
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3.5. X-ray crystallography
A dark yellow crystal of 1 with approximate dimen-
sions of 0.30 · 0.10 · 0.10 mm was selected for analysis.
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KM4CCD diffractometer with graphite-monochro-
mated Mo Ka radiation generated from an X-ray tube
operated at 50 kV and 35 mA. The images were indexed,
integrated, and scaled using the KUMA data reduction
package [9]. The crystal data, data collection parame-
ters, and results of the analysis are given in Table 1.
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using SHELXS97 [10] and refined by the full-matrix
least-squares method on all F2 data [11]. Nonhydrogen
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[5] (a) R.B. King, A. Fronzaglia, Inorg. Chem. 5 (1964) 1837;
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(1995) 335;

690
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3
˚
˚
(d) J.M. Oh, S.J. Geib, N.J. Cooper, Acta Crystallogr., Sect. C 54
(1998) 581;
c = 13.3438(9) A, b = 110.182(6)ꢁ, V = 1457.7(2) A , T = 100 K,
d = 1.182 g cmÀ3, l = 144 cmÀ1, Z = 4, monoclinic, space group
P21/c, final residuals: R1 = 0.0492, wR2 (I > 2r(I)) = 0.1309,
GOF = 1.78, Kuma KM4CCD diffractometer, radiation Mo Ka
(e) M.V. Baker, M.R. North, J. Organomet. Chem. 565 (1998)
225;
´
(f) T. Szymanska-Buzar, K. Kern, J. Organomet. Chem. 622
˚
(k = 0.71073 A).
[9] Oxford Diffraction Poland Sp., CCD Data Collection and
(2001) 74;
(g) H. Sun, Z. Chen, X. Zhou, Inorg. Chim. Acta 355 (2003) 404.
Reduction GUI, Version 1.173.13 beta (Release 14.11.2003)
Copyright 1995–2003.
[6] G.L. Geoffroy, M.S. Wrighton, Organometallic Chemistry, Aca-
demic Press, New York, CA, 1979, p. 59.
[10] G.M. Sheldrick, SHELXS97, Program for Crystal Structure Solu-
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[8] Crystal data of Ph3SiH: C18H16Si, M = 259, colorless crystals,
[11] G.M. Sheldrick, SHELXL97, Program for Crystal Structure
Refinement, University of Go¨ettingen, Germany, 1997.
˚
˚
crystal size 0.1 · 0.1 · 0.2 mm, a = 10.1284(7) A, b = 11.4912(7) A,