Synthesis of half-sandwich tungsten chlorogermyl and chlorostannyl complexes

Article abstract of DOI:10.1002/ejic.200700292

The reaction of the dichlorogermane Me₂GeCl₂ and stannanes R₂SnCl₂ (R = Me, Bu) with the alkali tungsten salts M[(η⁵-C₅R′₅)L(OC)₂W] (L = CO, PPh₃; M = Li, Na; R′ = H, Me) yields via alkali salt elimination a range of novel chlorostannyl- and chlorogermyl-functionalized tungsten complexes of the general formula [(η⁵-C ₅R′₅)L(OC)₂W(ER₂Cl)] (R′ = H, Me; L = CO, PPh₃; E = Ge, Sn; R = Me, Bu) (3a-e). The use of the phosphane-substituted tungsten anion Na[(η⁵-C ₅Me₅)(Ph₃P)(OC)₂W] (1c) and Me ₂SnCl₂ leads to a mixture consisting of the mono- (3e) as well as the di-substituted stannyl compound [{(η⁵-C ₅H₅)(Ph₃P)(OC)₂W} ₂(SnMe₂)] (4). Access to 3a is also given by reaction of ClMe₂Sn-C₅H₅ (5) with [(MeCN) ₃W(CO)₃] which includes chemoselective tin shift from the cyclopentadiene to the tungsten atom. In addition, a successive chlorination of [(η⁵-C₅H₅)(OC)₃W(SnMe ₃)] (6) via [(η⁵-C₅H₅)(OC) ₃W(SnMe₂Cl)] (3a) and [(η⁵-C ₅H₅)(OC)₃W(SnMeCl₂)] (7) to [(η⁵-C₅H₅)(OC)₃W(SnCl ₃)] (8) is presented. All new compounds have been fully characterized by elemental analyses and in solution by IR and multinuclear NMR spectroscopy. The crystal structures of complexes 3b-d and 8 were presented and discussed, showing bond lengths of 2.6272(4) A for Ge-W, 2.7959(5) (3b), 2.7866(3) (3d) and 2.7244(3) (8) A for the Sn-W bonds. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

Full text of DOI:10.1002/ejic.200700292

FULL PAPER
DOI: 10.1002/ejic.200700292
Synthesis of Half-Sandwich Tungsten Chlorogermyl and Chlorostannyl
Complexes
Holger Braunschweig,*[a] Holger Bera,[a] Barbara Geibel,[a] Rainer Dörfler,[a] Daniel Götz,[a]
Fabian Seeler,[a] Thomas Kupfer,[a] and Krzysztof Radacki[a]
Keywords: Half-sandwich complexes / Tungsten complexes / Germanes / Stannanes / Stannylcyclopentadienes
The reaction of the dichlorogermane Me2GeCl2 and stann-
anes R2SnCl2 (R = Me, Bu) with the alkali tungsten salts
M[(η5-C5RЈ5)L(OC)2W] (L = CO, PPh3; M = Li, Na; RЈ = H,
Me) yields via alkali salt elimination a range of novel chlo-
rostannyl- and chlorogermyl-functionalized tungsten com-
plexes of the general formula [(η5-C5RЈ5)L(OC)2W(ER2Cl)]
(RЈ = H, Me; L = CO, PPh3; E = Ge, Sn; R = Me, Bu) (3a–e).
The use of the phosphane-substituted tungsten anion Na[(η5-
C5Me5)(Ph3P)(OC)2W] (1c) and Me2SnCl2 leads to a mixture
consisting of the mono- (3e) as well as the di-substituted
stannyl compound [{(η5-C5H5)(Ph3P)(OC)2W}2(SnMe2)] (4).
Access to 3a is also given by reaction of ClMe2Sn–C5H5 (5)
with [(MeCN)3W(CO)3] which includes chemoselective tin
shift from the cyclopentadiene to the tungsten atom. In ad-
dition,
successive chlorination of [(η5-C5H5)(OC)3W-
a
(SnMe3)] (6) via [(η5-C5H5)(OC)3W(SnMe2Cl)] (3a) and [(η5-
C5H5)(OC)3W(SnMeCl2)] (7) to [(η5-C5H5)(OC)3W(SnCl3)] (8)
is presented. All new compounds have been fully charac-
terized by elemental analyses and in solution by IR and mul-
tinuclear NMR spectroscopy. The crystal structures of com-
plexes 3b–d and 8 were presented and discussed, showing
bond lengths of 2.6272(4) Å for Ge–W, 2.7959(5) (3b),
2.7866(3) (3d) and 2.7244(3) (8) Å for the Sn–W bonds.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2007)
and O as donor atoms) and the transition-metal bound
Cl3Sn moiety giving a sixfold-coordinated tin centre[7] (Fig-
ure 1).
Introduction
The first germanium and tin complexes of molybdenum
and tungsten have been prepared in the 1960’s[1] and since
that time [M]–SnR3 bonds are ubiquitous up to the present
day.[2] The chemistry of such complexes has been the object
of extensive studies due to their potential in many catalytic
and stoichiomtric processes.[3] Two important reactions of
transition-metal stannyl complexes [M]–SnR3 (R = organic
group) are the chlorination with hydrogen halides[4] and the
stanna-tropic shift from the transition-metal to the cyclo-
pentadienyl ligand in half-sandwich complexes, induced by
a strong base.[5] Despite this fact, the amount of complexes
owing a chlorogermyl or chlorostannyl moiety, which allow
further functionalization and reaction chemistry, is fairly
limited – in particular in the case of germanium, and only
little work has been carried out concerning investigations
of the Cl–Sn unit of a transition metal. One of them – the
most recent work – deals with chloride displacement by nu-
cleophilic sulfur or oxygen groups with the latter (pyridine-
dicarboxylic acid) leading to an iron complex with fivefold-
coordinated tin[6] (Figure 1). Another investigation topic is
the Lewis basicity of the Cl3Sn group. In this context, some
interestingmolybdenum and tungsten ansa complexes were
built up showing an intramolecular Lewis acid–base inter-
action of a cyclopentadienyl-bound donor group (with N
Figure 1. Iron and tungsten half-sandwich complexes with fivefold-
and sixfold-coordinated tin atoms.
Nevertheless, with regard to the facile chemistry of
R3ECl (E = Ge, Sn) which includes a wide variety of reac-
tions with alkali metals, organolithium compounds, hydrox-
ides, sulfides, Lewis bases, amides, alkoxides, etc., it seems
self-evident that much of it can be yet transferred to chlo-
rogermyl and chlorostannyl transition-metal complexes.
[a] Institut für Anorganische Chemie, Universität Würzburg,
Am Hubland, 97074, Würzburg, Germany
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Half-Sandwich Tungsten Chlorogermyl and stannyl Complexes
FULL PAPER
In an extension of our work on the reactivity of boryl-, chlorination chemistry which allows the facile synthesis of
borylene-,[8] or diborane(4)yl[9] moieties linked to half- tungsten complexes with mono, di- and trichlorinated stan-
sandwich metal fragments (e.g. compound [(η5-C5Me5)- nyl ligands.
(OC)2Fe–(BX2ǟpy)] (X = Cl, Br; py = pyridine),[8f] [(η5-
C5H5)(R3P)(OC)2W–{B(NMe2)–B(NMe2)Cl}] (R = Me,
Ph)[9a] in Figure 2) which included the addition of Lewis
Results and Discussion
bases to BCl2 ligands[8f,8i] analogous to Cl3Sn complexes,
The complexes of the general formula [(η5-C5RЈ5)L(OC)2-
we became interested in some aspects of the chemistry of
W(ER2Cl)] (RЈ = H, Me; L = CO, PPh3; E = Ge, Sn; R =
Me, Bu) (3a–e) are obtained from the corresponding dichlo-
rogermanes and stannanes R2ECl2 (E = Ge, Sn; R = Me,
Bu) (2a–c) with the alkali tungsten salts M[(η5-C5RЈ5)-
L(OC)2W] (L = CO, PPh3; M = Li, Na; RЈ = H, Me) (1a–
c) after 16–22 h reaction time at ambient temperature in
diethyl ether, according to Equation (1). The new com-
pounds are isolated as yellow and dark yellow (3e and 3a,b),
ochre (3d) and brown (3c) powders in yields between 70%
(3b) and 85% (3d). These results demonstrate that the syn-
thetic method chosen is straightforward and widely variable
and hence should give access to a range of analogue com-
plexes. 3a–e show moderate solubility in pentane or hexane
and dissolve readily in diethyl ether and aromatic solvents.
They can be stored under argon atmosphere at –30 °C for
several months without signs of decomposition. 3d can be
even stored at ambient temperature.
corresponding halogermyl and stannyl complexes.
The reaction of the triphenylphosphane-substituted
tungsten anion 1c with dichlorodimethylstannane (2b) does
not give exclusively 3e. Instead, a product mixture of 3e and
the dinuclear complex 4 is obtained (Figure 3). The ratio of
3e and 4 is determined by integration of the 1H NMR spec-
Figure 2. Methylpyridine Lewis base adduct of a X2B-substituted
iron complex and phosphane-substituted diborane(4)yl tungsten
half-sandwich complex.
In this paper we report on the synthesis, spectroscopic
and structural characterisation of the novel chlorodiorgano
germyl and stannyl complexes of tungsten. The synthetic
method chosen is straightforward and widely variable and
so should give access to a range of analogue complexes.
Additionally, we have developed three convenient and new
methods for a facile preparation of 3a, and established a Figure 3. Disubstituted dimethylstannane trans-4.
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H. Braunschweig et al.
FULL PAPER
trum and amounts to 2:1. The formation of 3e and 4 pro- crystallize in triclinic (3b) and monoclinic (3c,d) crystal sys-
¯
ceeds stereospecifically and only the trans-products are ob- tems with space groups P1 (3b), P21/c (3c) and C2/c (3d),
served, which is consistent with the synthesis of the parent respectively.
[(η5-C5H5)(Ph3P)(OC)2W(SnMe3)].[10] Due to the different
solubility in hexane both compounds can be easily sepa-
rated from each other. This reaction demonstrates the
higher nucleophilic character of the phosphane-substituted
tungsten anion 1c in comparison to the tricarbonyl deriva-
tive (1b) in spite of its higher steric demands.
All new complexes were characterised in solution by IR
and multinuclear NMR spectroscopy. The complexes 3a,c–
e show singlets for the dimethyl groups attached to the ger-
manium and tin atom in the 1H NMR spectra between 0.87
(3a) and 1.17 (3c) ppm, characteristic for an element nu-
cleus being deshielded with respect to those of the starting
dichlorogermane and stannanes. These values are in good
agreement to the corresponding signal found for [{H2C(O)-
C(η5-C5H4)}(OC)3W(SnMe2Cl)]2 (δ = 0.95 ppm).[11] The
signals of the Sn-bound methyl moieties are accompanied
2
by 117/119Sn satellites showing JHCSn coupling constants of
Figure 4. Molecular structure of [(η5-C5H5)(OC)3W(SnBu2Cl)] (3b)
45.3, 47.3 (3a), 42.5, 44.4 (3d) and 40.2, 41.8 (3e) Hz, thus
in the solid state with the atom-numbering scheme. Displacement
reflecting the increasing electron density of the tungsten
ellipsoids are drawn at the 50% probability level and the hydrogen
atoms have been omitted for clarity. Selected bond lengths [Å] and
fragments in this row. The 119Sn NMR resonances of 3a,d,e
are detected in close proximity at 227.0 (3a), 233.0 (3d) and
233.8 (3e) ppm, whereas the one of the butyl derivative 3b
differs significantly and appears at δ = 26.7 ppm due to the
electron-releasing effect of the butyl groups. Only in two
angles [°]: W1–C1 1.983(7), W1–C3 1.984(8), W1–C2 1.985(7), W1–
Sn1 2.7959(5), Sn1–C31 2.156(7), Sn1–C21 2.168(8), Sn1–Cl1
2.4203(18), C31–Sn1–C21 114.6(3), C31–Sn1–Cl1 99.1(2), C21–
Sn1–Cl1 99.6(2), C31–Sn1–W1 120.56(19), C21–Sn1–W1 114.1(2),
Cl1–Sn1–W1 104.34(5).
1
cases the JSnW coupling was observed amounting to 162.8
(3b) and 347.0 Hz (3d). Due to the fact that in the case of
3e and 4 the trans-product is exclusively formed, in the 31P
NMR spectra appears in each case one resonance at 38.61
(3e) and 44.50 ppm (4), accompanied by 183W [1JWP
=
293.6 Hz (3e), 267.3 Hz (4)] and 117/119Sn satellites [2JSnWP
= 123.9 and 128.8 Hz (3e), 125.4 and 130.8 Hz (4)]. As ex-
pected, 3a,c,d show three CO-stretching frequencies (A(1)Ј,
AЈЈ and A(2)Ј) each in the IR spectra between 1901 and
2010 cm–1, as expected for such tungsten complexes.[11] Sur-
prisingly, the butyl derivative 3b shows only two bands
(1999 and 1981 cm–1), one of which, however, is thus poss-
ibly indicating an overlap of two bands. In contrast, the
observed number of two CO-stretching frequencies for 3e
and 4 is in agreement with phosphane-substituted tungsten
stannyl complexes, as loss of a carbonyl group usually de-
creases the number of absorption bands from 3 to 2. As
expected, the carbonyl stretching frequencies decrease in
comparison to 3a,c,d and are found for 3e and 4 at 1904,
1835 and 1901, 1832 cm–1, respectively which lie very close
to those of [(η5-C5H5)(Ph3P)(OC)2W(SnMe3)].[10]
Figure 5. Molecular structure of [(η5-C5Me5)(OC)3W(GeMe2Cl)]
(3c) in the solid state with the atom-numbering scheme. Displace-
ment ellipsoids are drawn at the 50% probability level and the hy-
drogen atoms have been omitted for clarity. Selected bond lengths
[Å] and angles [°]: W1–C1 1.971(4), W1–C2 1.982(4), W1–C3
1.982(4), W1–Ge1 2.6272(4), Ge1–C31 1.948(4), Ge1–C32 2.008(3),
Ge1–Cl1 2.2428(10), C1–W1–Ge1 70.04(11), C2–W1–Ge1
123.98(11), C3–W1–Ge1 72.07(12), C31–Ge1–C32 106.44(17),
C31–Ge1–Cl1 101.62(13), C32–Ge1–Cl1 101.97(10), C31–Ge1–W1
117.55(13), Cl1–Ge1–W1 109.74(3).
X-ray diffraction analyses. The molecular structures of
[(η5-C5H5)(OC)3W(SnBu2Cl)] (3b), [(η5-C5Me5)(OC)3W-
(GeMe2Cl)] (3c) and [(η5-C5Me5)(OC)3W(SnMe2Cl)] (3d)
have been confirmed by X-ray diffraction studies and are
presented in Figure 4, Figure 5, and Figure 6. Selected bond
lengths and angles are listed below each Figure and crystal
The coordination sphere around each tungsten atom can
data and refinement parameters in Table 2 in the experi- be considered as a pseudo square-pyramid, with the three
mental section. In all cases, crystals, suitable for X-ray carbonyl ligands [mean W–C 1.984 (3b), 1.978 (3c) and
analysis, are obtained upon slow evaporation of saturated 1.978 Å (3d)] and the germyl or rather stannyl group form-
benzene solutions at room temperature. The compounds ing the base, while the aromatic ring systems occupie the
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Half-Sandwich Tungsten Chlorogermyl and stannyl Complexes
FULL PAPER
coordinated tin atoms, e.g. 2.404(1) and 2.459(2) Å in the
tungsten complex in Figure 1.[7] As expected, the tetrahe-
dral coordination geometry of the tin atoms of 3b,d is sig-
nificantly distorted almost to the same extent as already
mentioned for the Ge analogue and thus, angles between
99.1(2) (C31–Sn1–Cl1) and 120.56(19) (C31–Sn1–W1) (3b)
or rather 99.75(12) (C5–Sn1–Cl1) and 118.56(11) Å (C5–
Sn1–W1) (3d) were found. Interestingly, in both compounds
the W–Sn–C angles are widened whereas the C–Sn–Cl
angles are more acute in comparison to the ideal tetrahe-
dron angle. This characteristic could also be observed in the
Ge compound and was found in diorganostannyl molybde-
num complexes, too.[11,13] In 3b, there is an interaction of
one carbonyl oxygen (O1) with a hydrogen atom of the sec-
ond molecule of the same cell (H51A) which can be classi-
fied as moderate hydrogen bond according to the value of
2.508 Å (O1···H51A).
Figure 6. Molecular structure of [(η5-C5Me5)(OC)3W(SnMe2Cl)]
(3d) in the solid state with the atom-numbering scheme. Displace-
Alternative syntheses of 3a and chlorination reactions.
ment ellipsoids are drawn at the 50% probability level and the hy- Even though the following compounds were already men-
drogen atoms have been omitted for clarity. Selected bond lengths
tioned in literature, not all of them have been isolated and
[Å] and angles [°]: W1–C3 1.976(4), W1–C1 1.977(3), W1–C2
their characterisation has not been carried out to full ex-
1.982(4), W1–Sn1 2.7866(3), Sn1–C5 2.146(4), Sn1–C4 2.157(4),
tent. For example, up to now, it was only possible to obtain
Sn1–Cl1 2.4215(10), C5–Sn1–C4 107.61(16), C5–Sn1–Cl1
the di-chlorinated complex 7 together with 3a as an insepa-
rable mixture by treatment of 6 with hydrogen chloride.[4]
Therefore, we developed new and convenient syntheses for
these chlorostannyl compounds, isolated them and com-
99.75(12), C4–Sn1–Cl1 100.48(13), Cl1–Sn1–W1 108.97(3), C5–
Sn1–W1 118.56(11), C4–Sn1–W1 118.31(12).
apical position (“four-legged piano stool” complex). In the pleted their characterization.
case of 3c,d, the five methyl groups are slightly bent out of
One alternative route leading to 3a proceeds via the chlo-
the plane of the cyclopentadienyl ligand [mean 6.7° (3c) and rodimethylstannyl-cyclopentadiene 5 which is literature-
6.5° (3d)]. All these structural parameters lie in the range known,[14] but was here synthesized in a more convenient
reported in literature for comparable compounds.[7,11,12] way. The alkali salt elimination of sodium cyclopentadien-
The base-forming angles lie all between 70 and 75°. The ide and dichlorodimethylstannane yields after 18 h stirring
determined W–Ge distance amounts to 2.6272(4) Å, which at ambient temperature 5 according to Scheme 1. 5 is ob-
is about 0.1 Å shorter than the values in the PMe3-substi- tained as a yellow oil in 84% and can be stored at –30 °C
tuted trichlorogermanium complexes cis- and trans-[(η5- under Ar atmosphere over a period of months. Due to the
C5Me5)(Me3P)(OC)2W(GeCl3)]
[2.559(5)
(cis)
and fast stannatropic shift of the ClMe2Sn group with respect
2.5159(14) Å (trans)].[12a] This finding supports the observa- to the NMR time-scale, a singlet at δ = 5.99 ppm is ob-
tion that increased electron density at a central transition served for the cyclopentadiene protons at ambient tempera-
metal atom – evoked by the introduction of a phosphane ture. This chemical shift agrees very well with the literature
ligand – strengthens the transition metal–element bond. data (δ = 6.02 ppm[14a]) and the signal shows the expected
The determined Ge–C bond lengths are 1.948(4) (Ge1–C31)
and 2.008(3) (Ge1–C32) Å. For the germanium–chlorine
bond a length of 2.2428(10) Å is found, which is only
slightly longer than the corresponding bonds in the Cl3Ge
derivative [mean 2.206 (cis) and 2.199 Å (trans)].[12a] The
tetrahedral coordination geometry of the germanium atom
is strongly distorted indicated by angles in the range from
101.62(13) (C31–Ge1–Cl1) to 117.55(13)° (C31–Ge1–W1).
Only Cl1–Ge1–W1 shows an almost ideal tetrahedron angle
[109.74(3)°].
The determined W–Sn bond lengths are 2.7959(5) (3b)
and 2.7866(3) Å (3d), thus being in the range of tin-substi-
tuted tricarbonyl tungsten complexes.[7,11] The Sn–C bonds
of 3b are slightly longer [2.168(8) (Sn1–C21) and 2.156(7) Å
(Sn1–C31)] than those of 3d [2.146(4) (Sn1–C5) and
Scheme 1. Alternative synthesis of 3a via the chlorostannyl-func-
2.157(4) Å (Sn1–C4)]. For the tin–chlorine bonds, distances
tionalized cyclopentadiene 5 which is obtained from alkali salt eli-
of 2.4203(18) (3b) and 2.4215(10) Å (3d) are found, which
is very similar to those in tungsten complexes with sixfold- nane.
mination of sodium cyclopentadienyl and dichlorodimethyl stan-
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H. Braunschweig et al.
FULL PAPER
tin satellites with coupling constants of 29.0 and 30.0 Hz. a period of six days. 8 can be obtained in 60% as a yellow
In the 119Sn NMR spectrum a singlet is observed at δ = powder, which can be also exposed to air for a prolonged
101.45 ppm.[14b]
period without decomposition. The detected 1H NMR
In the last step, 5 is treated with [(MeCN)3W(CO)3] in chemical shift at 5.77 for the Cp is in accordance with litera-
refluxing THF over a period of 18 h, leading to 3a in 90% ture (δ = 5.6 ppm) as well as the IR data.[16] The 119Sn
yield (Scheme 1). 3a is obtained as an analytically pure yel- NMR resonance was detected at δ = –89.4 ppm, which is
low solid. The reaction proceeds chemoselectively and only about 115 ppm shifted to higher field in comparison to the
the chlorostannyl group shifts to the tungsten centre – no Mo analogue [(η5-C5H5)(OC)3Mo(SnCl3)] (δ = 26 ppm).[6]
complex tungsten hydride is observed as by-product. This Due to the fact that only IR data of 7 are published[16]
1
insertion of a coordinatively unsaturated transition-metal (except for H NMR of 8,[16b]), we characterized 7 and 8
1
fragment (W) into a Sn–C bond which is accompanied by by H, 13C and 119Sn NMR as well as elemental and melt-
oxidation of the W centre has precedence but only for tri- ing point analysis. Some of these data are listed in Table 1.
methylgermanium- and -tin-functionalized cyclopentadi-
enes.[15] In contrast, in Me3Si-substituted cyclopentadienes
Table 1. NMR spectroscopic features depending on the chlorina-
tion degree of the W-bound tin atom.[a]
the Si–C unit tends to remain intact due to a stronger and
less polar bond.[15a]
[WpSnMe3] [WpSnMe2Cl] [WpSnMeCl2] [WpSnCl3]
(6)
(3a)
(7)
(8)
Besides, we developed not only a selective synthesis of 7,
but also a controlled, successive chlorination of the trimeth-
ylstannyl tungsten complex 6 to the trichlorostannyl deriva-
tive 8 (Scheme 2) via isolable intermediates.
The first Me/Cl exchange is achieved by use of exactly
one equivalent of SnCl4 at ambient temperature, leading af-
ter two hours exclusively to 3a. After work up, 3a can be
obtained analytically pure in 92% yield. The second chlori-
nation is realized with a further equivalent of SnCl4 at am-
1H(MeSn) 0.51
0.87
227.0
47.3, 45.3
1.11
–
119Sn
42.3[b]
198.9[c]
46.2, 45.2
–89.4
–
2JHCSn
48.4, 46.4
[a] NMR spectroscopic data in ppm (in C6D6, except 8: CDCl3),
coupling constants in Hz. For a more detailed discussion of the IR
data and bonding energies see ref.[16a]. Wp ϵ (η5-C5H5)(OC)3W. [b]
1
1JSnW = 150.5 Hz. [c] JSnW = 596.8 Hz.
For better comparison of the compounds of 6, 3a, 7 and
1
bient temperature, too. The reaction is finished after two 8, we determined the H and 119Sn NMR chemical shifts
2
hours and yields 7 in 88%. The di-chlorination product 7 and the coupling constants JHCSn of the Sn-attached
can also be obtained directly from 6 if an excess of SnCl4 methyl groups (Table 1). The trends of the 1H NMR chemi-
is employed. 7 is characterized by a high stability even cal shifts in the row [(η5-C5H5)(OC)3W(SnMe3)] (6),
towards concentrated hydrochloric acid. For the tin-bound [(η5-C5H5)(OC)3W(SnMe2Cl)] (3a), [(η5-C5H5)(OC)3W-
methyl group a singlet at δ = 1.11 ppm is observed, showing (SnMeCl2)] (7) and [(η5-C5H5)(OC)3W(SnCl3)] (8) are very
the expected 117/119Sn satellites of 45.2 and 46.2 Hz, respec- regular and behave as expected – the more electronegative
tively. The 119Sn signal is detected at δ = 198.9 ppm. An chlorine atoms are bound at the tin atom the higher is the
2
excess of SnCl4 in refluxing chloroform gives access to the detected chemical shift value. Parallel, the JHCSn coupling
trichlorostannyl complex 8, when the mixture is heated over constants (MeSn) decrease continuously. In contrast to
Scheme 2. Stepwise chlorination of 6 via mono- and dichlorinated stannyl tungsten complexes 3a and 7 leading to the trichlorostannyl
complex 8 and direct synthesis of 7 and 8.
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Half-Sandwich Tungsten Chlorogermyl and stannyl Complexes
FULL PAPER
these findings, the 119Sn NMR shifts display no regular num case. Additionally, we found a short distance of
trend, and after the first Me/Cl substitution a maximum 2.925 Å between the chlorine atom Cl2 and the proton
shift value of 227.0 ppm is observed. Further chlorine sub- bound to C14, which can be classified as a weak, intramo-
stitution leads to a decrease of the 119Sn chemical shift up lecular hydrogen bond interaction.
to –89.4 ppm for 8. Apparently, two effects are responsible
It is known that organotin halides tend to build up asso-
for this feature namely the electronegative character of chlo- ciated arrangements with formation of σ-donor bridges in
rine as well as the π-back bonding of the p-lone pairs of the the solid state. It is interesting that 8 shows not such a inter-
chlorine. The latter effect increases with a growing number molecular association behaviour. Presumably, this finding is
of chlorine atoms due to the fact that the Lewis acid charac- caused by the transition-metal fragment but it remains open
ter of the tin atom is increasing at the same time.
whether steric or electronic effects are responsible.
X-ray diffraction analysis. The molecular structure of
[(η5-C5H5)(OC)3W(SnCl3)] (8) has been confirmed by X-
ray diffraction study and is depicted in Figure 7. Selected Conclusions
bond lengths and angles are listed below the Figure and
We were able to show that the alkali salt elimination has
crystal data and refinement parameters in Table 2 in the
experimental section. Suitable crystals are obtained upon
slow evaporation of saturated CDCl3 solution at room tem-
perature. 8 crystallizes in a triclinic crystal system with
to be regarded as a straightforward route to synthesize
chlorogermyl and chlorostannyl tungsten complexes and al-
lows the variation of the organo groups being attached to
the element as well as the transition-metal fragment itself.
The chlorination degree of the transition-metal bound tin
atom can be varied successively and selectively by use of
SnCl4. Thus, the work reported in this paper opens the door
to a range of chlorogermyl and chlorostannyl tungsten
complexes which enables further investigations of the chem-
ical behaviour, e.g. with respect to alkali metals, organo-
lithium compounds, hydroxides, sulfides, Lewis bases,
amides or alkoxides.
¯
space group P1.
Experimental Section
All manipulations were conducted either under an atmosphere of
dry argon or in vacuo using standard Schlenk line or glovebox
techniques. Solvents (benzene and pentane) were purified by distil-
lation from appropriate drying agents (sodium and sodium wire)
under dry argon, immediately prior to use. C6D6 was degassed by
three freeze-pump-thaw cycles and stored over molecular sieves. IR
spectra were recorded as CH2Cl2 solutions between KBr plates on a
Bruker Vector 22 FT-IR spectrometer. 1H, 31P{1H} and 119Sn{1H}
NMR spectra were acquired on a Bruker Avance 200 NMR spec-
trometer at 200.1, 121.5 and 111.9 or 186.5 MHz, respectively and
referenced to external TMS or SnMe4 (119Sn). 13C{1H} NMR spec-
tra were recorded on a Bruker AMX 400 NMR spectrometer at
125.8 MHz and referenced to the solvent. Microanalyses for C, H
Figure 7. Molecular structure of [(η5-C5H5)(OC)3W(SnCl3)] (8) in
the solid state with the atom-numbering scheme. Displacement el-
lipsoids are drawn at the 50% probability level and the hydrogen
atoms have been omitted for clarity. Selected bond lengths [Å] and
angles [°]: W1–C1 1.998(5), W1–C2 2.011(5), W1–C3 2.001(4), W1–
Sn1 2.7244(3), Sn1–Cl1 2.3450(11), Sn1–Cl3 2.3616(11), Sn1–Cl2
2.3681(11), C1–W1–Sn1 126.42(12), C3–W1–Sn1 75.08(12), C2–
W1–Sn1 76.17(12), Cl1–Sn1–Cl3 96.41(4), Cl1–Sn1–Cl2 98.94(4),
Cl3–Sn1–Cl2 99.45(4), Cl1–Sn1–W1 121.81(3), Cl3–Sn1–W1
119.57(3), Cl2–Sn1–W1 116.14(3).
and
N were performed by Mrs. L. Michels (University of
Würzburg) on a Vario Micro instrument (Elementar Analysensys-
teme). Starting materials were prepared according to literature pro-
cedures: Li[W(η5-C5H5)(CO)3][17] (1a), [(η5-C5Me5)(OC)3WCl],[18]
[(η5-C5H5)(OC)3WSnMe3][1b] (6) and [(MeCN)3W(CO)3].[19] The
reagents Me2GeCl2 (2a), Me2SnCl2 (2b), SnCl4 and Bu2SnCl2 (2c)
were purchased from commercial sources and not further purified
prior use.
8 shows the typical piano-stool arrangement as expected
for a half-sandwich compound. The geometrical features of
8 in the solid state are very similar to that found for the
Mo analogue [(η5-C5H5)(OC)3Mo(SnCl3)]:[6] the tetrahe-
dral coordination geometry of the tin atom is strongly dis-
torted and resemble a trigonal pyramid also found for the
Mo compound. All Cl–Sn–Cl angles are acute (mean:
98.27°) whereas the Cl–Sn–W angles are more obtuse show-
ing values between 116.14(3) (Cl2–Sn1–W1) and 121.81(3)°
(Cl1–Sn1–W1). Not only the Sn–Cl distances (mean:
2.358 Å) are similar to those of the Mo complex, but also
the transition-metal–tin distances, which amount to
Preparation of Starting Material
1. Li[W(η5-C5Me5)(CO)3] (1b)
Lithium Tricarbonyl(pentamethylcyclopentadienyl)tungstate
A solution of 1.80 g (4.45 mmol) of (η5-C5Me5)(OC)3WH in 15 mL
Et2O was treated with 2.09 mL (5.35 mmol) of BuLi (2.5 ) at 0 °C.
The color of the solution changed from yellow to brown and after
15 min 1b started to precipitate. The mixture was stirred for 1.5 h
2.7244(3) Å in the tungsten and 2.7223(4) in the molybde- at ambient temperature. After reaction the precipitate consisting of
Eur. J. Inorg. Chem. 2007, 3416–3424
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3421

H. Braunschweig et al.
FULL PAPER
1b was filtered off, washed twice with 10 mL of hexane and finally
dried in vacuo. Yield 1.64 g (4.01 mmol; 90%). Pale brown, pyro-
phoric powder. Elemental analysis was not carried out due to the
pyrophoric behaviour of 1b.
2. [(η5-C5Me5)(Ph3P)(OC)2WCl] (9)
Dicarbonyl(chloro)(η5-pentamethylcyclopentadienyl)(triphenylphos-
10 mL diethyl ether. The mixture was stirred at ambient tempera-
ture overnight. The ether was removed under reduced pressure and
the oily residue was extracted with pentane (3ϫ10 mL). The com-
bined extracts were filtered through celite and the filtrate was evap-
orated to dryness. The sticky residue was washed with ice-cold pen-
tane (3ϫ2 mL) and was dried in vacuo. Yield 526 mg (0.88 mol,
70 %). Dark yellow powder. M.p. 74 °C. 1H NMR (300 MHz,
C6D6): δ = 4.82 (s, 5 H, Cp), 1.91–1.73 (m, 8 H, CH2-CH2), 1.55–
1.52 (m, 4 H, SnCH2), 1.05 (t, 6 H, CH3) ppm. 13C{1H} NMR
(75.5 MHz, C6D6): δ = 88.43 (s, Cp), 31.64 (s, CH2), 27.40 (s, CH2),
phanyl)tungsten(II)
A solution of 3.20 g (7.30 mmol) of [(η5-C5Me5)(OC)3WCl] and
1.91 g (7.30 mmol) PPh3 in 10 mL benzene in was irradiated with
UV light for 5 d. The solvent was removed in vacuo, the crude
residue washed with 20 mL hexane and the product dried in vacuo.
Yield 4.11 g (6.11 mmol, 84 %). Orange powder. 1H NMR
(300.4 MHz, C6D6): δ = 7.62–7.52 (m, 6 H, Ph), 7.08–6.98 (m, 9 H,
Ph), 1.65 (s, 15 H, C5Me5) ppm. 13C{1H} NMR (75.5 MHz, C6D6):
δ = 250.75 (d, 2JCWP = 18.5 Hz, cis-CO), 237.99 (d, 2JCWP = 7.3 Hz,
trans-CO), 135.85 (d, 1JCP = 47.4 Hz, ipso-C6H5), 132.28 (d, 3JCCCP
19.24 (s, CH2), 13.69 (s, CH3) ppm. 119Sn{1H} NMR (111.9 MHz,
1
C6D6): δ = 26.7 (s, JSnW = 162.8 Hz) ppm. IR (hexane): ν(C=O)
˜
= 1999 (m), 1981 (m) cm–1. C16H23ClO3SnW (601.35): calcd. C
31.96, H 3.86; found C 32.29, H 3.99.
3. [(η5-C5Me5)(OC)3W(GeMe2Cl)] (3c)
Tricarbonyl(chlorodimethylgermyl)(η5-pentamethylcyclopentadien-
4
yl)tungsten(II)
= 10.1 Hz, meta-C6H5), 130.95 (d, JCCCCP = 2.4 Hz, para-C6H5),
128.69 (d, 2JCCP = 9.0 Hz, ortho-C6H5), 112.80 (d, 2JCWP = 1.2 Hz,
0.52 g (1.27 mmol) of Li[W(η5-C5Me5)(CO)3] (1b) were suspended
in 10 mL Et2O and treated with 0.18 mL (1.27 mmol, 0.22 g) of
Me2GeCl2. The reaction mixture was stirred for 22 h at ambient
temperature. After reaction LiCl was filtered off by use of a celite
pad. The filtrate was evaporated to dryness giving a dark brown
residue which was washed with 3 mL hexane at –40 °C and dried
in vacuo. Yield 0.56 g (81%). Brown solid, m.p. 62 °C. 1H NMR
(200.1 MHz, C6D6): δ = 1.71 [s, 15 H, C5(CH3)5], 1.17 [s, 6 H,
Ge(CH3)2] ppm. 13C{1H} NMR (75.5 MHz, C6D6): δ = 217.95 (s,
CO-trans), 202.29 (s, CO-cis), 102.52 (s, C5Me5), 28.67 [s, Ge-
H3CC5), 11.00 (s, H3CC5) ppm. 31P{1H} NMR (121.5 MHz,
1
C6D6): δ = 26.57 (s, JPW = 274.6 Hz) ppm. IR (Et O): ν(C=O) =
˜
2
1947 (vs), 1870 (m) cm–1. C30H30ClO2PW (672.82): calcd. C 53.55,
H 4.49; found C 53.68, H 4.66.
3. Na[W(η5-C5Me5)(CO)2(PPh3)] (1c)
Sodium Dicarbonyl(η5-pentamethylcyclopentadienyl)(triphenylphos-
phanyl)tungstate
Na amalgam was prepared by dissolving 0.28 g (12.22 mmol) so-
dium in 50 g mercury. 35 mL THF were added and then 4.11 g
(6.10 mmol) of [(η5-C5Me5)(Ph3P)(OC)2WCl] (9). The reaction
mixture was stirred for 18 h at ambient temperature. The suspen-
sion was separated from the sodium amalgam and the solvents
evaporated to dryness. The crude solid was washed with three
10 mL portions of hexane and dried in vacuo. Yield 3.75 g
(5.67 mmol, 93 %). Yellow-green, pyrophoric powder. 1H NMR
(300.4 MHz, [D8]THF): δ = 7.84–7.82 (m, 6 H, Ph), 7.13–7.02 (m,
(CH ) ], 9.00 [s, C (CH ) ] ppm. IR (hexane): ν(C=O) = 2003 (s),
˜
3 2
5
3 5
1931 (s), 1907 (s) cm–1. C15H21ClGeO3W (541.23): calcd. C 33.29,
H 3.91; found C 32.62, H 3.81.
4. [(η5-C5Me5)(OC)3W(SnMe2Cl)] (3d)
Tricarbonyl(chlorodimethylstannyl)(η5-pentamethylcyclopentadi-
enyl)tungsten(II)
To a suspension of 0.66 g (1.16) of Li[W(η5-C5Me5)(OC)3] (1b) in
20 mL Et2O were added 0.36 g (1.64 mmol) of Me2SnCl2 and the
reaction mixture stirred for 17 h at ambient temperature. After re-
action LiCl was filtered off over celite and the filtrate evaporated
to dryness. The crude brown product was washed with 5 mL of
hexane at –40 °C and dried in vacuo. Yield 0.80 g (85%). Ochre
solid, m.p. 122 °C. 1H NMR (200.1 MHz, C6D6): δ = 1.70 (s, 15
4
9 H, Ph), 1.89 (s, JHCCWP = 29.4 Hz, 5 H, Cp) ppm. 31P{1H}
NMR (121.5 MHz, C6D6): δ = 31.44 (s, 1JPW = 278.9 Hz) ppm. IR
(THF): ν (C=O) = 1780 (s), 1729 (s) cm–1. C30H30NaO2PW
˜
(660.36). Elemental analysis was not carried out due to the pyro-
phoric behaviour of 1c.
Preparation of Germyl and Stannyl Tungsten Complexes
1. [(η5-C5H5)(OC)3W(SnMe2Cl)] (3a)
Tricarbonyl(chlorodimethylstannyl)(η5-cyclopentadienyl)tungsten(II)
2
H, C5Me5), 0.91 [s, JHCSn = 42.5 and 44.4 Hz, 6 H, (H3C)2Sn]
ppm. 13C{1H} NMR (125.8 MHz, C6D6): δ = 220.89 (s, CO-trans),
217.87 (s, CO-cis), 103.70 (s, C5Me5), 10.71 [s, C5(CH3)5], 2.48 [s,
1JCSn = 245.5 and 259.9 Hz, Sn(CH3)2] ppm. 119Sn NMR
(186.5 MHz, C6D6): δ = 233.04 [s, 1JWSn = 347.0 Hz] ppm. IR (hex-
To a suspension of 635 mg (1.87 mmol) of Li[W(C5H5)(CO)3] (1a)
in 10 mL diethyl ether were added 411 mg (1.87 mmol) of
Me2SnCl2 and the mixture was stirred at ambient temperature over-
night. The solvent was removed in vacuo and the residue was ex-
tracted with of hexane (3ϫ10 mL). The combined extracts were
filtered through celite and the filtrate was evaporated to dryness.
Yield 793 mg (1.53 mol, 72%). Dark yellow powder. M.p. 91 °C.
ane): ν(C=O) = 1901 (s), 1927 (s), 1997 (s) cm–1. C H ClO SnW
˜
15 21
3
(587.33): calcd. C 30.67, H 3.60; found C 30.34, H 3.67.
5. [(η5-C5Me5)(OC)2(Ph3P)W(SnMe2Cl)] (3e) and {[(η5-C5Me5)-
(OC)2(Ph3P)W]2(SnMe2)} (4)
Dicarbonyl(trimethylstannyl)(η5-pentamethylcyclopentadienyl)(tri-
phenylphosphanyl)tungsten(II)
600 mg (0.83 mmol) of Na[W(η5-C5Me5)(OC)2(PPh3)] (1c) were
suspended in 20 mL Et2O and treated with 183 mg (0.83 mmol) of
Me2SnCl2. The reaction mixture was stirred for 16 h at ambient
temperature and NaCl filtered through by use of a celite pad. The
filtrate was evaporated to dryness and the residue consisting of 3e
and 4 extracted with 25 mL of hexane. 3e dissolves readily in hex-
ane whereas 4 remains as an yellow solid which was dried in vacuo.
2
1H NMR (300 MHz, C6D6): δ = 4.52 (s, 5 H, Cp), 0.87 (s, JHCSn
= 47.3, 45.3 Hz, 6 H, SnMe2) ppm. 13C{1H} NMR (75.5 MHz,
C6D6): δ = 89.04 (s, Cp), 2.99 (s, SnMe2) ppm. 119Sn{1H} NMR
(111.9 MHz, C D ): δ = 227 (s) ppm. IR (hexane): ν(C=O) = 2010
˜
6
6
(m), 1940 (m), 1911 (m) cm–1. C10H11ClO3SnW (517.20): calcd. C
23.22, H 2.14; found C 23.44, H 2.24.
2. [(η5-C5H5)(OC)3W(SnBu2Cl)] (3b)
(Dibutylchlorostannyl)(tricarbonyl)(η5-cyclopentadienyl)tungsten(II)
Similar to paragraph 1. above, from 570 mg (1.68 mmol) of The combined hexane extracts were concentrated and crystallized
Li[W(C5H5)(CO)3] (1a) and 380 mg (1.25 mmol) of Bu2SnCl2 in at –30 °C. The hexane phase was separated and the solid dried in
3422
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© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2007, 3416–3424

Half-Sandwich Tungsten Chlorogermyl and stannyl Complexes
FULL PAPER
vacuo. 3e: Yield 340 mg (0.42 mmol, 51 %). Yellow solid, m.p.
87 °C. H NMR (200.13 MHz, C6D6): δ = 7.68–7.43 (m, 6 H, Ph),
ppm. C7H11ClSn (249.32): calcd. C 33.72, H 4.45; found C 33.34,
H 4.67.
7. [(η5-C5H5)(OC)3W(SnMe2Cl)] (3a) by Reaction of 5 with
1
2
7.09–6.93 (m, 9 H, Ph), 1.68 (s, 15 H, Me5C5), 1.05 [s, JHCSn
=
40.2 and 41.8 Hz, 6 H, MeSn] ppm. 13C{1H} NMR (75.5 MHz,
[(MeCN)3W(CO)3]
2
1
C6D6): δ = 230.06 [d, JCP = 132.3 Hz, CO], 134.54 [d, JCP
=
46.6 Hz, ipso-C6H5], 134.29 [d, 1JCP = 10.0 Hz, meta-C6H5], 130.53
A suspension of 450 mg (1.80 mmol) of C5H5SnMe2Cl (5), 704 mg
(1.80 mmol) of [(MeCN)3W(CO)3] and 10 mL THF was refluxed
over the period of 18 h. After cooling to room temperature, all
volatiles were removed in vacuo and the residue was extracted with
hexane (3ϫ10 mL). The hexane extracts were combined and fil-
tered through a celite pad. The filtrate was concentrated and stored
at –70 °C over the period of one week. The hexane phase was re-
moved and the solid dried in vacuo. Yield 837 mg (1.62 mmol,
90%). Yellow solid.
3
2
[d, JCCCP = 2.4 Hz, para-C6H5], 128.56 [d, JCCP = 9.9 Hz, ortho-
1
C6H5], 101.16 [s, JCW = 5.4 Hz, C5Me5], 11.25 (s, C5Me5), 2.88 (s,
CH3Sn) ppm. 31P{1H} NMR (121.5 MHz, C6D6): δ = 38.61 [s,
1JPW = 293.6, 2JPWSn = 128.8 und 123.9 Hz] ppm. 119Sn{1H} NMR
2
(300.13 MHz, C6D6): δ = 233.80 [d, JSnWP = 132.1 Hz] ppm. IR
(Et O): ν(C=O) = 1904 (vs), 1835 (vs) cm–1. C32H36ClO2PSnW
˜
2
(821.60): calcd. C 46.78, H 4.42; found C 46.67, H 4.25.
1
4: Yield 138 mg (0.11 mmol, 13%). Yellow solid, m.p. 123 °C. H
8. [(η5-C5H5)(OC)3W(SnMe2Cl)] (3a) by Reaction of 6 with SnCl4
NMR (300.4 MHz, C6D6): δ = 7.68–7.43 (m, 6 H, Ph), 7.09–6.93
(m, 9 H, Ph), 1.78 (s, 30 H, Me5C5), 0.91 [d, 4JHCSnWP = 1.2, 2JHCSn
= 44.0 and 48.0 Hz, 6 H, H3CSn] ppm. 31P{1H} NMR (121.5 MHz,
A solution of 270 mg (0.54 mmol) of [(η5-C5H5)(OC)3W(SnMe3)]
(6) in 5 mL benzene was treated with 142 mg (0.54 mmol) of SnCl4
and the mixture was stirred at ambient temperature for 2 h. All
volatiles were removed in vacuo and the residue was extracted with
hexane (3ϫ19 mL). The combined extracts were filtered through
celite and the filtrate was evaporated to dryness. Yield 258 mg
(0.50 mmol, 92%). Dark yellow powder.
1
2
C6D6): δ = 44.50 [s, JPW = 267.3, JPWSn = 130.8 und 125.4 Hz]
ppm. IR (Et O): ν (C=O) = 1901 (vs), 1832 (vs) cm– 1
.
˜
2
C52H46O4P2SnW2 (1283.26): calcd. C 48.67, H 3.61; found C 48.47,
H 4.05.
6. C5H5SnMe2Cl (5)
9. [(η5-C5H5)(OC)3W(SnMeCl2)] (7) by Reaction of 3a with SnCl4
Tricarbonyl(dichloromethylstannyl)(η5-cyclopentadienyl)tungsten(II)
A solution of 258 mg (0.50 mmol) of [(η5-C5H5)(OC)3W-
(SnMe2Cl)] (3a) in 5 mL diethyl ether was treated slowly with
131 mg (0.50 mmol) of SnCl4 at 0 °C and the mixture was stirred
(Chlorodimethylstannyl)cyclopentadiene
A suspension of 418 mg (4.75 mmol) of NaCp and 15 mL Et2O
was treated with 1.04 g (4.75 mmol) of Me2SnCl2. The mixture was
stirred for 18 h at ambient temperature and NaCl was removed by
filtration through a celite pad. The filtrate was evaporated under
reduced pressure (70 mbar) at ambient temperature. Yield 1.00 g at ambient temperature for 2 h. All volatiles were removed in vacuo
(4.01 mmol, 84%). Yellow oil. 1H NMR (200.1 MHz, C6D6): δ =
and the residue was extracted with Et2O (2ϫ10 mL). The com-
bined extracts were filtered through celite and the filtrate was evap-
3
2
5.99 (s, JHCCSn = 30.0 and 29.0 Hz, 5 H, C5H5), 0.03 [s, JHCSn
=
59.2 and 56.8 Hz, 6 H, (H3 C)2 Sn] ppm. 1 3 C{1 H} NMR orated to dryness. Yield 237 mg (0.44 mmol, 88%). Yellow powder.
(125.8 MHz, C6D6): δ = 114.91 (s, 1JCSn = 96.8 Hz, C5H5Sn), –2.96 M.p. 189 °C. 1H NMR (300 MHz, C6D6): δ = 4.49 (s, 5 H, Cp),
[s, (H3C)2Sn] ppm. 119Sn NMR (186.5 MHz, C6D6): δ = 101.45 (s)
1.11 (s, JHCSn = 46.2, 45.2 Hz, 3 H, SnMe2) ppm. 13C{1H} NMR
2
Table 2. Crystal data and refinement parameters for the compounds 3b–d and 8.
Compound
3b
3c
3d
8
Empirical formula
Formula weight (gmol–1
Temperature [K]
Radiation, λ [Å]
Crystal system
Space group
Unit cell dimensions
a [Å]
b [Å]
c [Å]
α [°]
β [°]
C16H23ClO3SnW
601.33
100(2)
C15H21ClGeO3W
541.21
193(2)
C15H21ClO3SnW
587.31
173(2)
C8H5Cl3O3SnW
558.01
97(2)
)
0.71073 (Mo-Kα)
triclinic
monoclinic
P21/c
monoclinic
C2/c
triclinic
¯
¯
P1
P1
7.8200(6)
11.4910(9)
21.0814(16)
79.768(3)
89.533(3)
89.927(3)
1864.2(2)
4
8.2325(5)
25.4316(15)
9.4108(6)
90.00
111.8140(10)
90.00
1829.21(19)
4
1.965
30.036(3)
8.3148(7)
17.7603(15)
90.00
122.8430(10)
90.00
3726.6(5)
8
2.094
7.7851(3)
8.2946(3)
11.1925(4)
93.7950(10)
108.7020(10)
108.2510(10)
638.90(4)
2
γ [°]
Volume [Å3]
Z
Calculated density (gcm–3
)
2.143
7.657
1136
2.901
11.563
504
Absorbtion coefficient [mm–1
F(000)
]
8.078
1032
7.658
2208
Theta range for collection
Reflections collected
Independent reflections
Refinement method
Data/parameters
0.98 to 31.95°
88054
11465
2.46 to 26.08°
3624
3481
2.30 to 26.39°
24318
1.95 to 26.08°
15287
2513
6061
Full-matrix last-squares on F2
11465 –397/6
1.138
3624/190
1.170
3826/190
1.096
2513/145
1.088
Goodness-of-fit on F2
Final R indices [IϾ2σ(I)]
R Indices (all data)
R1 = 0.0497, wR2 = 0.1287 R1 = 0.0205, wR2 = 0.0509
R1 = 0.0532, wR2 = 0.1342 R1 = 0.0217, wR2 = 0.0514
R1 = 0.0198, wR2 = 0.0462 R1 = 0.0234, wR2 = 0.0605
R1 = 0.0215, wR2 = 0.0469 R1 = 0.0238, wR2 = 0.0608
Eur. J. Inorg. Chem. 2007, 3416–3424
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3423

H. Braunschweig et al.
FULL PAPER
(75.5 MHz, C6D6): δ = 215.16 (s, trans-CO), 211.89 (s, JCW
1
[2] M. S. Holt, W. L. Wilson, J. H. Nelson, Chem. Rev. 1989, 89,
11.
[3] a) T. Szymanska-Buzar, T. Gtowiak, Polyhedron 1998, 17, 3419;
b) L. Benczene, G. Szalai, T. L. Overton, Inorg. Chim. Acta
1997, 254, 5; c) T. Szymanska-Buzar, T. Gtowiak, J. Or-
ganomet. Chem. 1995, 489, 207; d) P. K. Baker, Adv. Or-
ganomet. Chem. 1996, 40, 45.
[4] R. E. J. Bichler, H. C. Clark Hunter, A. T. Rake, J. Organomet.
Chem. 1974, 69, 367.
[5] a) J. Cervantes, St. P. Vincenti, R. N. Kapoor, K. H. Pannell,
Organometallics 1989, 8, 744; b) W. K. Dean, W. A. G. Gra-
ham, Inorg. Chem. 1977, 16, 1061.
=
=
1
1
144.6 Hz, cis-CO), 89.91 (s, JCW = 4.9 Hz, Cp), 11.46 (s, JCSn
7.7 Hz, MeSn) ppm. 119Sn{1H} NMR (111.9 MHz, C6D6): δ =
198.88 (s, 1JWSn = 596.8 Hz) ppm. C9H8Cl2O3SnW (537.61): calcd.
C 20.11, H 1.50; found C 20.03, H 1.80.
10. [(η5-C5H5)(OC)3W(SnMeCl2)] (7) by Reaction of 6 with 2 Equiv.
of SnCl4
Analogously to paragraph 9., from 320 mg (0.64 mmol) of [(η5-
C5H5)(OC)3W(SnMe3)] (6) and 335 mg (1.28 mmol) of SnCl4 in
10 mL diethyl ether over the period of 4 h. Yield 242 mg (0.45 mol,
90%). Yellow powder.
11. [(η5-C5H5)(OC)3W(SnCl3)] (8) by Reaction of 7 with SnCl4 (ex.)
Tricarbonyl(trichlorostannyl)(η5-cyclopentadienyl)tungsten(II)
[6] J. L. Neto, G. M. Lima, A. O. Porto, J. D. Ardisson, A. C. Do-
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[8] For reviews seea) H. Braunschweig, C. Kollann, D. Rais, An-
gew. Chem. 2006, 118, 5380; Angew. Chem. Int. Ed. 2006, 45,
5254; b) H. Braunschweig, Adv. Organomet. Chem. 2004, 51,
163; c) H. Braunschweig, M. Colling, Eur. J. Inorg. Chem. 2003,
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223, 1; e) H. Braunschweig, Angew. Chem. 1998, 110, 1882;
Angew. Chem. Int. Ed. 1998, 37, 1786. For selected examples
on the reactivity of metal bound boron halides see:; f) H.
Braunschweig, K. Radacki, F. Seeler, G. R. Whittell, Organo-
metallics 2006, 25, 4605; g) H. Braunschweig, K. Radacki, D.
Rais, D. Scheschkewitz, Angew. Chem. 2005, 117, 5796; Angew.
Chem. Int. Ed. 2005, 44, 5651; h) H. Braunschweig, K. Rad-
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127, 1386; i) H. Braunschweig, K. Radacki, D. Rais, G. R.
Whittell, Angew. Chem. 2005, 117, 1217; Angew. Chem. Int. Ed.
2005, 44, 1192; j) H. Braunschweig, M. Müller, Chem. Ber./
Recueil 1997, 130, 1295.
To a suspension of 266 mg (0.49 mmol) of [(η5-C5H5)(OC)3W-
(SnMeCl2)] (7) in 10 mL chloroform were added 1.28 mg
(4.90 mmol) of SnCl4 and the mixture was heated and stirred under
reflux over the period of 6 d. All insoluble material was filtered off
and the solvent and unreacted SnCl4 were removed in vacuo. The
residue was washed with hexane (3ϫ10 mL) and the solvents evap-
orated to dryness. Yield 164 mg (0.29 mol, 60%). Yellow powder.
1
3
M.p. 91 °C. H NMR (300 MHz, CDCl3): δ = 5.77 (s, JHCWSn
=
3.4 Hz, 5 H, Cp) ppm. 13C{1H} NMR (75.5 MHz, CDCl3): δ =
89.17 (s, Cp) ppm. 119Sn{1H} NMR (111.9 MHz, CDCl3): δ =
–89.4 (s) ppm. C8H5Cl3O3SnW (558.03): calcd. C 17.22, H 0.90;
found C 17.44, H 1.24.
12. [(η5-C5H5)(OC)3W(SnCl3)] (8) by Reaction of 6 with SnCl4 (ex.)
Tricarbonyl(trichlorostannyl)(η5-cyclopentadienyl)tungsten(II)
[9] a) H. Braunschweig, H. Bera, D. Götz, K. Radacki, Z. Natur-
forsch., Teil B 2006, 61, 29; b) H. Braunschweig, M. Koster,
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Hinz, Polyhedron 1998, 17, 1103; b) A. C. Filippou, J. G. Win-
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Chem. 1998, 9, 169.
Analogously to paragraph 11., from 326 mg (0.60 mmol) of [(η5-
C5H5)(OC)3W(SnMe3)] (6) and 1.28 mg (4.90 mmol) of SnCl4 in
15 mL chloroform over the period of 6 d. Yield 148 mg (0.26 mol,
55%). Yellow powder.
Crystal Structure Determination: The crystal data of 3b–d and 8
(Table 2) were collected with a Bruker A2 diffractometer with
a CCD area detector and multi-layer mirror monochromated Mo-
Kα radiation. The structures were solved by direct methods, refined
with the Shelx software package (G. Sheldrick, University of
Göttingen, 1997) and expanded using Fourier techniques. All non-
hydrogen atoms were refined anisotropically. Hydrogen atoms were
assigned idealized position and were included in structure factor
calculations.
[10]
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Chem. 1969, 19, P5.
CCDC-644418 (for 3b), -636078 (for 3c), -636079 (for 3d) and
-640077 (for 8) contain the supplementary crystallographic data for
this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
[16] a) H. Willemen, L. F. Wuyts, D. F. Van der Vondel, G. P.
Van der Kelen, J. Electron Spectrosc. Relat. Phenom. 1977, 11,
245; b) F. Bonati, S. Cenini, R. Ugo, J. Chem. Soc. A 1967,
932.
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[18] Th. Straub, M. Haukka, M. Brunner, A. M. P. Koskinen, T. A.
Pakkanen, J. Organomet. Chem. 2005, 690, 674–677.
[19] F. Edelmann, P. Behrens, S. Behrens, U. Behrens, J. Organomet.
Chem. 1986, 310, 333.
Acknowledgments
We thank Deutsche Forschungsgemeinschaft (DFG) and Fonds der
Chemischen Industrie (FCI) for financial support.
[1] a) D. J. Cardin, S. A. Keppie, M. F. Lappert, Inorg. Nucl.
Chem. Lett. 1968, 4, 365; b) H. R. H. Patil, W. A. G. Graham,
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Chem. Soc. 1964, 179.
Received: March 15, 2007
Published Online: June 6, 2007
3424
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Eur. J. Inorg. Chem. 2007, 3416–3424