The oxidative addition of SnCl4 to [W(CO)4(NCMe)(PPh3)]. The X-ray crystal structure of [WH(CO)3(NCMe)(PPh3)2]- [SnCl5·MeOH]

Article abstract of DOI:10.1016/S0277-5387(02)01043-4

The oxidative addition reaction of SnCl₄ with [W(CO)₄(NCMe)(PPh₃)] in acetonitrile gives a mixture of seven-]coordinate tungsten(II) compounds: [WCl(SnCl₃)(CO)₃(NCMe)(PPh₃)] (1), [WCl₂(CO)₃(NCMe)(PPh₃)] (2), [WCl(SnCl₃)(CO)₂(NC-Me)₂(PPh₃)] (3), and [WCl₂(CO)₂(NCMe)₂(PPh₃)] (4) identified by IR and NMR (¹H, ¹³C{¹H}, and ³¹P{¹H}) studies. Treatment of [W(CO)₄(NCMe)(PPh₃)] with 1 equiv. of SnCl₄ in CH₂Cl₂ solution besides compounds 1 and 2 also gives ionic species such as [HPPh₃]⁺ and [SnCl₆]^2- and cationic tungsten(II) complexes. The crystal structure of one of these, [WH(CO)₃(NCMe)(PPh₃)₂][SnCl₅ ·MeOH] (5), has been established by single-crystal X-ray diffraction. The IR, ¹H, ¹³C{¹H} and ³¹P{¹H} spectra of 5 are also described and can be correlated with the crystallographically observed geometry. A notable feature of 5 is the presence of an agostic interaction of the hydride ligand with one of the carbonyl ligands.

Full text of DOI:10.1016/S0277-5387(02)01043-4

Polyhedron 21 (2002) 1817ꢂ1823
/
www.elsevier.com/locate/poly
The oxidative addition of SnCl4 to [W(CO)4(NCMe)(PPh3)].
The X-ray crystal structure of [WH(CO)3(NCMe)(PPh3)2]-
[SnCl5×
/
MeOH]
Teresa Szyman´ska-Buzar *, Tadeusz G lowiak, Izabela Czelus´niak
Faculty of Chemistry, University of Wroc law, ul. F. Joliot-Curie 14, 50-383 Wroc law, Poland
Received 8 February 2002; accepted 29 April 2002
Abstract
The oxidative addition reaction of SnCl4 with [W(CO)4(NCMe)(PPh3)] in acetonitrile gives a mixture of seven-coordinate
tungsten(II) compounds: [WCl(SnCl3)(CO)3(NCMe)(PPh3)] (1), [WCl2(CO)3(NCMe)(PPh3)] (2), [WCl(SnCl3)(CO)2(NC-
Me)2(PPh3)] (3), and [WCl2(CO)2(NCMe)2(PPh3)] (4) identified by IR and NMR (1H, 13C{1H}, and 31P{1H}) studies. Treatment
of [W(CO)4(NCMe)(PPh3)] with 1 equiv. of SnCl4 in CH2Cl2 solution besides compounds 1 and 2 also gives ionic species such as
[HPPh3]ꢀ and [SnCl6]2ꢁ and cationic tungsten(II) complexes. The crystal structure of one of these,
1
[WH(CO)3(NCMe)(PPh3)2][SnCl5×
/
MeOH] (5), has been established by single-crystal X-ray diffraction. The IR, H, 13C{1H} and
31P{1H} spectra of 5 are also described and can be correlated with the crystallographically observed geometry. A notable feature of 5
is the presence of an agostic interaction of the hydride ligand with one of the carbonyl ligands. # 2002 Elsevier Science Ltd. All
rights reserved.
Keywords: Tungsten; Tin; Oxidative addition; Crystal structures; Hydride; NMR
1. Introduction
CMe)(PPh3)] [8] with SnCl4. We expected tungsten(II)
compounds containing phosphine ligands to show a
different catalytic activity compared with nitrile com-
pounds. A compound of this type, [WI2(CO)3(NC-
Me)(PPh3)], was synthesized previously by Baker et al.
in reaction of [WI2(CO)3(NCMe)2] with 1 equiv. of PPh3
[9] and then its structure was determined by X-ray
The preparation and properties of seven-coordinate
compounds containing weakly coordinated nitrile li-
gands has been of continuing interest for some years [1ꢂ
/
7]. The reasons for this interest are first that such
compounds may serve as versatile starting materials in
the synthesis of other seven-coordinate complexes and
second that they have potential catalytic activity for
crystallography [10]. However, WÃ
/
Sn compounds con-
taining phosphine ligands appear very labile and diffi-
cult to isolate in pure crystalline form [11]. The
trichlorostannyl ligand can be eliminated from the
coordination sphere of tungsten to give cationic com-
plexes of tungsten(II) with the tin atom in the counter-
ion [12]. Such an unprecedented cationic complex
polymerization and metathesis reactions [1ꢂ
Following the discovery [1,4ꢂ7] that Group 6 metal
complexes of the type [M(CO)4(NCMe)2] MꢃMo, W,
in reaction with metal halides M?Cl4, M?ꢃSn, Ge, give
the oxidative addition product [MCl(M?Cl3)(CO)3-
(NCMe)2], we have now investigated the formation of
/
7].
/
/
/
[WCl(CO)(tBuCÅ
was obtained during a reaction of [WCl(SnCl3)(CO)-
(tBuCÅ
CH)2(NCMe)] with 2 equiv. of PPh3 in CH2Cl2
/
CH)(NCMe)(PPh3)2]2[SnCl6]×
/
4NCMe
a related WÃ/Sn complex in reaction of [W(CO)4(N-
/
[12]. For this reason and because of the scarcity of X-ray
studies on ionic tungsten(II) seven-coordinate com-
pounds, an X-ray structural determination of the
cationic compound formed during the reaction of
[W(CO)4(NCMe)(PPh3)] with SnCl4 were undertaken.
* Corresponding author. Tel.: ꢀ
2348
E-mail address: tsz@wchuwr.chem.uni.wroc.pl (T. Szyman´ska-
Buzar).
/
48-71-375-7221; fax: ꢀ48-71-328-
/
0277-5387/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 2 7 7 - 5 3 8 7 ( 0 2 ) 0 1 0 4 3 - 4

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T. Szyman´ska-Buzar et al. / Polyhedron 21 (2002) 1817ꢂ1823
/
2. Results and discussion
the CO and PPh3 ligands in the above tungsten(II)
compounds.
Based on these spectral data, the formation of four
seven-coordinate
tungsten(II)
compounds:
2.1. Synthesis and spectroscopic characterization
[WCl(SnCl3)(CO)3(NCMe)(PPh3)] (1), [WCl2(CO)3(NC-
Me)(PPh3)] (2), [WCl(SnCl3)(CO)2(NCMe)2(PPh3)] (3),
and [WCl2(CO)2(NCMe)2(PPh3)] (4), can be proposed
(Scheme 1).
In reactions carried out in a coordinating solvent,
such as acetonitrile, we considered the oxidative addi-
tion of SnCl4 to [W(CO)4(NCMe)(PPh3)] followed by
the dissociation of SnCl2 and the displacement of the
CO ligands by the solvent (CH3CN) molecules. How-
ever, during the reaction of [WCl(SnCl3)(CO)3(NCMe)2]
with 1 equiv. of PPh3 in CH3CN, the formation of a
mixture of compounds 3 and 4 was detected due to the
presence of n(CO) bands characteristic for bis(carbonyl)
Reaction of [W(CO)4(NCMe)(PPh3)] with an equi-
molar quantity of SnCl4 in CH3CN produced a mixture
of oxidative addition products, i.e. tungsten(II) com-
pounds, as observed by 31P{1H} NMR spectra (Fig. 1).
Four signals at dP about 30 ppm indicate the formation
of four tungsten(II) compounds containing triphenyl-
phosphine ligands. The intensity ratio of these signals
changes slowly during the 1 week NMR measurement,
indicating some transformation processes in solution.
Two signals at dP 30.16 and 32.44, due to the presence of
117Sn (Iꢃ
and characteristic JPSn coupling constants in the range
308ꢂ348 Hz [13,14] can be assigned to tungsten(II)
Sn bond. The intensity of
/
1/2, 7.6%) and 119Sn (Iꢃ
/
1/2, 8.6%) satellites,
2
/
compounds [11,13ꢂ16]. Two pairs of n(CO) bands:
/
1913(m), 1840(vs) and 1935(m), 1864(vs) cmꢁ1, deriving
from compounds 3 and 4, respectively, were observed in
IR spectrum of a solid sample.
compounds containing a WÃ
/
these two signals decreases much faster in time than
others. Two other signals at dP 30.70 and 32.77 are due
to compounds without a WÃ
/
Sn bond, being the
Treatment of [W(CO)4(NCMe)(PPh3)] with 1 equiv.
of SnCl4 in CH2Cl2 solution besides compounds 1 and 2
also gave ionic species such as [HPPh3]ꢀ, [SnCl6]2ꢁ, and
cationic complexes of tungsten(II). One of the cationic
complex of tungsten(II) was isolated in crystalline form
and X-ray analysis showed it to be [WH(CO)3-
products of the elimination of SnCl2 species from the
trichlorostannyl ligand. It is interesting that for the
1
Sn bond the value of JPW
compounds without of a WÃ
/
ꢁ
/
150 and 170 Hz, respectively*
/
is much smaller than
the value of JPW for signals due to WÃSn compounds
(1JPW
222 and 235 Hz). This suggests stronger WÃ
1
/
ꢃ
/
/P
(NCMe)(PPh3)2][SnCl5×
/
MeOH] (5). The IR spectra
interactions in compounds containing trichlorostannyl
ligands than in analogues with chlorine ligands only.
(KBr disc) of compound 5 exhibit two sharp n(CO)
bands at 2040(w) and 1939(vs) cmꢁ1; this is fully
consistent with the unusual mer configuration of the
CO groups observed crystallographically. To our knowl-
edge, a similar arrangement of three carbonyl groups
has previously been detected only for [WCl(SnCl3)-
(CO)3(h4-NBD)] [17].
Three broad bands in the n(CO) region (2030ꢂ1840
/
cmꢁ1) of the IR spectra of these compounds suggest the
presence of compounds with two and three carbonyl
groups [11,13ꢂ
compounds show three groups of carbonyl carbon
signals in the region 232ꢂ227 ppm. The very narrow
/
16]. 13C{1H} NMR spectra of these
/
The appearance of two carbonyl resonances in the
13C{1H} NMR spectrum (125.8 MHz, 293 K) of 5 at an
ranges of dP suggest a similar mutually cis position of
intensity ratio of 2:1, at dCꢃ
/
212.09 and dCꢃ208.48,
/
respectively, conforms with the solid state structure of
the distorted capped octahedron and mer geometry of
the carbonyl groups. The 31P{1H} NMR spectrum
(121.5 MHz, 293 K) of 5 shows a broad resonance due
to 2 equiv. triphenylphosphine ligands at dP 25.04
(1JPW
5 exhibit a three-line resonance due to a hydride ligand
1
131 Hz). The H spectra (500 MHz, 293 K) of
ꢃ
/
Fig. 1. 31P{1H} NMR spectrum showing the mixture of four seven-
coordinate
tungsten(II)
compounds:
[WCl(SnCl3)(CO)3(NC-
Me)(PPh3)](1), [WCl2(CO)3(NCMe)(PPh3)] (2), [WCl(SnCl3)(CO)2-
(NCMe)2(PPh3)](3), and [WCl2(CO)2(NCMe)2(PPh3)](4) formed dur-
ing the reaction of [W(CO)4(NCMe)(PPh3)] and SnCl4 in acetonitrile.
The signals denoted by an asterisk (*) are due to 183W satellites and by
circle (k) are due to 117Sn and 119Sn satellites.
Scheme 1.

T. Szyman´ska-Buzar et al. / Polyhedron 21 (2002) 1817ꢂ
/
1823
1819
assigned to compounds 1ꢂ
/
4, were observed. The solu-
bility of [WCl2(CO)3(PPh3)2] in CD3CN is probably
extremely low.
The oxidative addition reaction of phosphine com-
plexes of tungsten(0) with SnCl4 carried out in dichlor-
omethane is always accompanied by the formation of
[HPPh3]ꢀ cations. The latter species gives a n(PH) band
at 2430 cmꢁ1 and other characteristic bands [26ꢂ
29] at
/
1
1114 and 721 cmꢁ1 in IR spectra. In H NMR spectra
of the reaction products containing [HPPh3]ꢀ cations, a
1
9.36 with JHP
doublet at dHꢃ
/
ꢃ526 Hz can be
/
detected.
Fig. 2. High field 1H NMR spectrum of the [WH(CO)3(NCMe)-
(PPh3)2][SnCl5×MeOH] (5) complex obtained at 293 K in CD2Cl2,
showing the hydride signal at dH 3.98.
From the experimental results we deduce that the
reaction course strongly depends on the solvent. When
the reaction is carried out in acetonitrile solution, the
elimination of SnCl2 from the coordination sphere of
tungsten occurs to give neutral compounds. In dichlor-
omethane solution, the elimination of SnCl3 anionic
ligands takes place yielding cationic compounds of
tungsten(II). The SnCl3 anion should be oxidized by
CH2Cl2 [30,31] producing the counterpart anion
[SnCl5]ꢁ or [SnCl6]2ꢁ
/
ꢃ/
ꢁ
/
at dHꢃ
/
ꢁ
/
3.98 (2JPH
ꢃ
/
40 Hz), which is further split due
13 Hz) and
32 Hz) (Fig. 2).
to a coupling to the tungsten atom (1JWH
ꢃ
/
ꢁ
to the carbonyl carbon atom (1JCH
ꢃ
/
1
The JWH
ꢃ13 Hz observed here is much smaller than
/
ꢁ
that for [nPr4N]4[H4W4(CO)12] (44.5 Hz [18]),
[Et4N]4[W2(CO)8(PMe2Ph)2] (44 Hz [19]), [Et4N][(m-
H)(m-Ph2P(CH2)4PPh2)W2(CO)8] (46.1 Hz [20]), and
[PPN][HW(CO)4(PMe3)] (54 Hz [21]). In contrast, the
.
2JPH
ꢃ/40 Hz is about two times higher than observed in
2.2. Structure of [WH(CO)3(NCMe)(PPh3)2][SnCl5×
MeOH] (5)
/
those tungsten(0) compounds [18ꢂ/21], but very close to
that found for tungsten(II) compounds such as
[WH(CO)3(PMe2Ph)3]ꢀ (47 Hz [22]) and [WH(SPh)-
(CO)3(PCy3)2] (43 Hz [23]). This suggests that the
electronic configuration of the metal atom (d6 or d4)
Fig. 3 shows an ORTEP perspective view of compound
5 that includes the atom numbering scheme. Selected
interatomic bond distances and angles are summarized
in Table 2. The crystal structure of 5 consists of well
separated [WH(CO)3(NCMe)(PPh3)2]ꢀ cations and
can exert influence on WÃ
satellites (Iꢃ1/2, 1%) observed on the hydride signal
suggest a CÃH interaction. The small hydrogenꢂcarbon
coupling constant indicates a three-center WÃHꢀ ꢀ ꢀC
/
H interactions. The 13C
/
[SnCl5×
/
MeOH]ꢁ anions. The tungsten atom is in a
/
/
/
agostic interaction [24,25], which was additionally
proved by X-ray structure investigations (see next
paragraph).
Similar spectral characteristic to those of compound 5
were shown by the product formed in the reaction of
trans-[W(CO)4(PPh3)2] and SnCl4 in CH2Cl2. Two
broad n(CO) bands at 2030(w) and 1937(vs) in the IR
spectrum, a signal at dPꢃ
31P{1H} NMR spectrum and two doublets at dCꢃ
218.36 (2JCP 213.75 (2JCP
32 Hz) and dCꢃ 9 Hz)
/
25.92 (1JPW
ꢃ138 Hz) in the
/
/
ꢃ
/
/
ꢃ
/
in the 13C{1H} NMR spectrum were observed. These
spectral data suggest the formation of the cationic
compound of tungsten(II) analogues to 5. This com-
pound has never been isolated in pure crystalline form,
so the counter-ion is unknown. However, during the
reaction of trans-[W(CO)4(PPh3)2] and SnCl4 in CH3CN
solution, the formation of [WCl2(CO)3(PPh3)2] as the
main product was observed by IR spectra, due to
characteristic n(CO) bands at 2014(s), 1936(vs), and
1894(s) cmꢁ1 [11]. In the 31P{1H} NMR spectra
(CD3CN, 293 K) of the reaction products, only very
Fig. 3. The crystal structure of [WH(CO)3(NCMe)(PPh3)2][SnCl5×
/
low-intensity signals in the range dPꢃ
/
32.77ꢂ30.16,
/
MeOH] (5).

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T. Szyman´ska-Buzar et al. / Polyhedron 21 (2002) 1817ꢂ1823
/
˚
e.g. 1.78 A in [WH(Cl)(CO)2(PMe3)3] [35] and 1.835(36)
seven-coordinate environment that can be approxi-
mately described [32,33] as capped octahedral, with the
hydride ligand H(2) capping the triangular face formed
by the carbon, nitrogen, and phosphorus atoms (Fig. 4).
Within the distorted octahedral description, the two
carbon atoms, two phosphorus atoms, and the nitrogen
˚
A in [WCl2(CHCMe3)(CO)(PMe3)2] [24]. The H(2)Ã
/
˚
C(2) distance in 5 is only 0.9992 A, indicative of a
three-centre WÃHꢀ ꢀ ꢀC agostic interaction [24,25]. The
H(2)ÃC(2)ÃW angle is 57.18 and the H(2)ÃWÃC(2)
/
/
/
/
/
angle is 29.38. Similar agostic interactions, but involving
the a-H of the neopentylidene ligand, have been detected
and the carbon atoms are mutually trans with C(2)Ã
C(3), P(1)ÃWÃP(2), and N(1)ÃWÃC(1) angles of
175.31(18)8, 164.90(4)8, and 160.57(17)8, respectively.
The capped octahedral face defined by the angles C(2)Ã
WÃN(1)ꢃ90.29(16)8, P(1)ÃWÃC(2)ꢃ88.13(3)8, and
P(1)ÃWÃN(1)ꢃ83.16(9)8 is a little larger than the
opposite face defined by P(2)ÃWÃC(3)ꢃ83.81(13)8,
C(3)ÃWÃC(1)ꢃ81.65(19)8, and P(1)ÃWÃC(1)ꢃ
78.79(14)8.
/
WÃ
/
in [WCl2(CHCMe3)(CO)(PMe3)2], where a CÃ
/
H dis-
/
/
/
/
˚
tance of 1.053(36) A, an HÃ
and an HÃWÃ
Interestingly, the carbonyl carbon atom adjacent to the
hydride ligand is associated with a little shorter CÃ
/
CÃ
/
W angle of 72.2(20)8,
/
/
C angle of 33.1(11)8 were observed [24].
/
/
/
/
/
/
/O
/
/
/
˚
length (1.128(5) A) than in the other two CO ligands
/
/
/
˚
(1.161(5) and 1.143(5) A).
/
/
/
/
/
/
The [SnCl5(MeOH)]ꢁ anion has irregular octahedral
geometry. The cis ClÃ
87.65(4)8ꢂ96.25(4)8, while the cis ClÃ
smaller (81.66(9)8ꢂ86.70(10)8), which is consistent with
chlorine having a greater van der Waals radius than
/
SnÃ
/
Cl angles fall in the range
The bond lengths from tungsten are not unusual and
are of the same order of magnitude as those reported in
/
/
SnÃO angles are
/
/
the literature for related complexes. For example, the
˚
P bond length of 2.54 A is only a little
average WÃ
/
˚
Cl(2) distance of 2.442(1) A is
oxygen. The Sn(2)Ã
/
˚
shorter than the values of 2.58 A (av.) found in the
complexes CH)(NCMe)(PPh3)2]2-
[WCl(CO)(tBuCÅ
[SnCl6]×4NCMe [12] and [WI2(CO)3(PEt3)2] [34]. The
average WÃ
mutually trans carbonyl ligands, is a little longer than a
significantly longer than the remaining four SnÃ
/Cl
/
˚
distances of 2.384 A (av.). This difference is readily
explained in terms of Clꢀ ꢀ ꢀH interactions. The Cl(2)
atom is involved in an intermolecular contact of 3.090(4)
/
˚
C bond length of 2.035 A, found for the two
/
˚
A to H(4). Thus, an alcohol ligand coordinated through
the oxygen atom to the tin atom is also hydrogen-
bonded to a Cl(2) atom of the SnCl5 counter-ion.
˚
C bond length of 1.971(5) A for a carbonyl ligand in
WÃ
/
the trans position to an acetonitrile ligand. This is in
accord with the higher trans influence of the CO group
as compared with the nitrile ligand. The WÃ
/
N bond
distance of 2.159(3) A is a little shorter than found in the
complexes CH)(NCMe)(PPh3)2]2-
[WCl(CO)(tBuCÅ
[SnCl6]×4NCMe (2.186(6) A [12]) and [WCl(SnCl3)-
(CO)3(NCMe)2] (2.18(1) A [4]). The WÃ
˚
3. Experimental
/
˚
/
3.1. General data
˚
/
H distance of
H distances
˚
1.713 A in 5 is a little shorter than the WÃ
/
All reactions were carried out under nitrogen by
standard Schlenk line techniques. The solvents and
reagents applied were dried, distilled, and deoxygenated.
Solution IR spectra were obtained using KBr or NaCl
plates, while solid samples were recorded using KBr
pellets on an FT IR model-400 Nicolet instrument. Far-
previously reported for the other tungsten(II) hydrides,
IR spectra were recorded (600ꢂ
100 cmꢁ1) with a Bruker
/
IFSv instrument in a Nujol mull on a polyethylene film.
1H, 13C{1H}, and 31P{1H} NMR spectra were recorded
on an AMX 300 and 500 MHz Bruker spectrometer.
Chemical shifts were referenced against solvent reso-
nance as the internal standard. In 1H NMR spectra
dHꢃ
/
1.98 for CD3CN and dHꢃ5.32 for CD2Cl2 and in
/
13C NMR spectra dCꢃ
/
118.00 for CD3CN and dCꢃ
/
54.00 for CD2Cl2. 31P NMR spectra were referenced
to external 85% H3PO4.
3.2. Synthesis of [W(CO)4(NCMe)(PPh3)] [8]
[W(CO)5(PPh3)] (1.05 g, 1.79 mmol), prepared ac-
cording to the published procedure [36], was dissolved in
acetonitrile (50 cm3) with continuous stirring under a
nitrogen atmosphere in a 100 cm3 round-bottomed flask
Fig. 4. The coordination sphere of tungsten(II) in [WH(CO)3-
(NCMe)(PPh3)2]ꢀ cation.

T. Szyman´ska-Buzar et al. / Polyhedron 21 (2002) 1817ꢂ
/
1823
1821
equipped with a quartz window through which the
solution was irradiated with an HBO 200 Hg lamp. The
course of the reaction was monitored by IR measure-
ments, and photolysis was stopped when the IR band of
[W(CO)5(PPh3)] at 2073 cmꢁ1 had decayed (about 3 h).
The solvent was evaporated in vacuum to yield a yellow
residue containing [W(CO)4(NCMe)(PPh3)] (90%),
[W(CO)3(NCMe)2(PPh3)], and [W(CO)5(PPh3)] identi-
ppm. Slow crystallization from CH2Cl2ꢂ
tolueneꢂheptane solution at approximately 273 K gave
yellow crystals, which were isolated and fully character-
ized as [WH(CO)3(NCMe)(PPh3)2][SnCl5×MeOH] (5).
Simultaneously precipitated colorless crystals were iden-
tified by X-ray analysis as [HPPh3]2[SnCl6] and cis-
[SnCl4(OPPh3)2] [37].
/
CH3OHꢂ
/
/
/
Anal. Calc. for C42H38Cl5NO4P2SnW: C, 43.39; H,
3.29; N, 1.20. Found: C, 43.30; H, 3.45; N, 1.28%. IR
(KBr disc): n(CN) 2287(vw), n(CO) 2040(w), 1939(vs)
fied by 31P{1H} NMR spectra in CD3CN due to
1
28.77, JPW
respective signals at dPꢃ
/
ꢃ240 Hz [8],
/
1
32.42, JPW
1
21.24, JPW
dPꢃ
/
ꢃ
/
222 Hz, and dPꢃ
/
ꢃ
/
242
cmꢁ1
(PPh3), dHꢃ
(HOMe),dHꢃ
1JHC 32 Hz. 13C{1H} NMR, (CD2Cl2, 293 K): dCꢃ
212.09 (2 CO), dCꢃ208.48 (1 CO), dCꢃ127.7
(CH3CN), dCꢃ35.81 (HOMe), dCꢃ5.11 (CH3CN).
31P{1H} NMR (CD2Cl2, 293 K): dPꢃ25.04, 1JPW
131
Hz.
.
1H NMR (CD2Cl2, 293 K): dHꢃ
/
7.90ꢂ/7.70d
Hz. Unreacted [W(CO)5(PPh3)] was removed from the
mixture by extraction to heptane.
/
5.85 (broad) (HOMe), dHꢃ
/
3.87 (broad)
1
2
/
ꢁ
/
3.97t, JHW
ꢃ/13 Hz, JPH
ꢃ40 Hz,
/
ꢃ
/
/
3.3. Oxidative addition of SnCl4 to
/
/
[W(CO)4(NCMe)(PPh3)]
/
/
/
ꢃ
/
3.3.1. Reaction in CH3CN solution
To [W(CO)4(NCMe)(PPh3)] (0.83 g, 1.38 mmol)
dissolved in 50 cm3 of acetonitrile was added SnCl4
(0.36 g, 1.38 mmol) by means of a syringe. The mixture
was stirred for 4 h, during which time the yellow
solution gradually changed to an orange color, while
the n(CO) frequency of the starting tungsten compound
disappeared. After the completion of the reaction, the
solution was evaporated to dryness and the residue
washed with heptane.
3.4. Reaction of [W(CO)4(PPh3)2] with SnCl4
To [W(CO)4(PPh3)2], prepared in photochemical
reaction of [W(CO)5PPh3] with PPh3 [38], (0.18 g, 0.22
mmol) in 25 cm3 of CH2Cl2, 2 equiv. of SnCl4 were
added (0.12 g, 0.46 mmol). After 48 h stirring, IR
spectroscopy confirmed the reaction to be complete.
Volatiles were removed in vacuum to yield an orange
solid, which was washed with heptane and dried. The IR
spectrum in a KBr disc showed two broad carbonyl
bands at 2030(m) and 1937(vs) cmꢁ1. The 31P{1H}
NMR spectra in CD2Cl2 showed the formation of a
mixture of new tungsten(II) compounds characterized
IR (KBr disc): n(CN) 2318(vw), 2287(vw) cmꢁ1
,
n(CO) 2031(w), 1935(vs), 1913(sh), 1859(sh), 1840(sh)
1
cmꢁ1; (Nujol): n(SnCl) broad 330(w) cmꢁ1. H NMR,
(CD3CN, 293 K): dHꢃ
(CH3CN). 13C{1H} NMR, (CD3CN, 293 K): dC 231.9,
230.69, 226.72 (CO), dCꢃ135.14ꢂ129.93d (PPh3).
31P{1H} NMR (CD3CN, 293 K): dPꢃ
/
7.80ꢂ
/
7.28 m (PPh3), dHꢃ2.17
/
/
/
by 31P signals at dPꢃ
(50%) and 25.63 (10%). Signal at dPꢃ
Hz (25%) indicates the formation of [W(CO)5(PPh3)]. In
/
28.94 (15%), 25.92, 1JPW
ꢃ
/
138 Hz
1
/
32.77, JPW
ꢃ
/
/
20.95, 1JPW
ꢃ
/
244
1
2
170 Hz, dPꢃ
2JPSn
341 and 348 Hz, dPꢃ
and dPꢃ
/
32.44, JPW
ꢃ
/
235 Hz, JPC
ꢃ
/
57 Hz,
1
30.70, JPW
ꢃ
/
/
ꢃ
/
150 Hz
2
57 Hz, JPSn
the 13C{1H} spectrum, two (2:1) doublets at dCꢃ
/
1
2
2
218.36, JCP
2
213.75, JCP
/
30.16, JPW
ꢃ
/
222 Hz, JPC
ꢃ
/
ꢃ
/
ꢃ
/
32 Hz and dCꢃ
/
ꢃ
/
9 Hz
308 and 320 Hz. These spectral data were assigned to the
following tungsten(II) compounds: [WCl(SnCl3)(CO)3-
(NCMe)(PPh3)] (1), [WCl2(CO)3(NCMe)(PPh3)] (2),
[WCl(SnCl3)(CO)2(NCMe)2(PPh3)] (3), and [WCl2-
(CO)2(NCMe)2(PPh3)] (4).
were observed. Two additional doublets (1:4) at dCꢃ
/
2
199.19, JCP
2
197.22, JCP
ꢃ
/
22 Hz and dCꢃ
/
ꢃ
/
7 Hz
proved the presence of [W(CO)5(PPh3)]. From a
CH2Cl2 solution of these compounds the colorless
crystals of [HPPh3]2[SnCl6] salts always precipitate. IR
spectra (KBr, disc):n(PH) 2430 cmꢁ1 and other char-
3.3.2. Reaction in CH2Cl2 solution
acteristic bands at 1114, 869, and 721 cmꢁ1 [26ꢂ
29].
/
To [W(CO)4(NCMe)(PPh3)] (0.9 g, 1.5 mmol) dis-
solved in 5 cm3 of CH2Cl2 was added SnCl4 (0.39 g, 1.5
mmol). After 2 h stirring, IR spectroscopy confirmed the
reaction to be complete. Volatiles were removed in
vacuum to yield an orange solid, which was washed with
heptane and dried. The IR spectrum in a KBr disc
showed two broad carbonyl bands at 2030(m) and
1930(vs) cmꢁ1, and a shoulder on the former band.
The 31P{1H} NMR spectra in CD2Cl2 showed the
formation of a mixture of compounds; very low-
intensity 31P signals, decaying over time, were observed
at dP about 30 ppm and intense signals at dP about 25
3.5. Reaction of [WCl(SnCl3)(CO)3(NCMe)2] with
PPh3 in CH3CN
To [WCl(SnCl3)(CO)3(NCMe)2] [4] (0.16 g, 0.3 mmol)
dissolved in 10 cm3 of acetonitrile was added PPh3 (0.7
g, 0.3 mmol) in 5 cm3 of acetonitrile. The mixture was
stirred for 25 min, during which time the n(CO)
frequency of the starting tungsten compound disap-
peared. After that time the solution was evaporated to
dryness and the orange residue washed with heptane.
Anal. Calc. for C24H21Cl4N2O2PSnW (3): C, 34.12; H,

1822
T. Szyman´ska-Buzar et al. / Polyhedron 21 (2002) 1817ꢂ
/
1823
2.51; N, 3.32. Found: C, 34.13; H, 2.68; N, 3.68%. IR
(KBr disc): n(CN) 2339(vw), 2295(vw); n(CO) 1935(m),
Table 2
˚
Selected bond lengths (A) and angles (8) for [WH(CO)3(NC-
Me)(PPh3)2][SnCl5×MeOH] (5)
1864(vs) cmꢁ1
;
235 Hz, JPSn
31P{1H} NMR (CD3CN): dPꢃ
/
32.44,
1JPW
ꢃ
/
ꢃ
/
341 and 348 Hz. After pro-
2
Bond lengths
longed reaction time in acetonitrile the purple crystals of
another bis(carbonyl) compound (4) were precipitated.
IR (KBr disc): n(CN) 2290(vw), n(CO) 1914(m),
W(1)ÃC(1)
W(1)ÃC(3)
W(1)ÃC(2)
W(1)ÃN(1)
W(1)ÃP(2)
W(1)ÃP(1)
W(1)ÃH(2)
C(2)ÃH(2)
O(1)ÃC(1)
O(2)ÃC(2)
O(3)ÃC(3)
Sn(2)ÃO(4)
Sn(2)ÃCl(5)
Sn(2)ÃCl(3)
Sn(2)ÃCl(1)
Sn(2)ÃCl(4)
Sn(2)ÃCl(2)
O(4)ÃC(4)
O(4)ÃH(4)
1.971(5)
2.033(5)
2.037(5)
2.159(3)
2.525(1)
2.550(1)
1.7132
1840(vs) cmꢁ1
.
3.6. Crystal and refinement data for compound 5
0.9992
1.161(5)
1.128(5)
1.143(5)
2.220(3)
2.380(1)
2.380(1)
2.384(1)
2.395(1)
2.442(1)
1.391(7)
0.92(6)
Crystal data and relevant refinement details for 5 are
presented in Table 1. The yellow crystals of 5 were
grown from
a
CH2Cl2ꢂ
/
CH3OHꢂ
/
tolueneꢂheptane
/
(5:0.1:1:10) solution. The crystals were stable enough
when handled in an inert atmosphere or coated with a
light hydrocarbon oil to protect them from the atmo-
sphere.
Crystal data for 5 were collected on a Kuma
KM4CCD k-axis diffractometer with graphite-mono-
Bond angles
˚
chromated Mo Ka radiation (lꢃ
/
0.71073 A), m(Mo
C(1)ÃW(1)ÃC(3)
C(1)ÃW(1)ÃC(2)
C(3)ÃW(1)ÃC(2)
C(1)ÃW(1)ÃN(1)
C(3)ÃW(1)ÃN(1)
C(2)ÃW(1)ÃN(1)
C(1)ÃW(1)ÃP(2)
C(3)ÃW(1)ÃP(2)
C(2)ÃW(1)ÃP(2)
N(1)ÃW(1)ÃP(2)
C(1)ÃW(1)ÃP(1)
C(3)ÃW(1)ÃP(1)
C(2)ÃW(1)ÃP(1)
N(1)ÃW(1)ÃP(1)
P(2)ÃW(1)ÃP(1)
C(1)ÃW(1)ÃH(2)
C(3)ÃW(1)ÃH(2)
C(2)ÃW(1)ÃH(2)
N(1)ÃW(1)ÃH(2)
P(2)ÃW(1)ÃH(2)
P(1)ÃW(1)ÃH(2)
O(2)ÃC(2)ÃH(2)
W(1)ÃC(2)ÃH(2)
O(4)ÃSn(2)ÃCl(5)
O(4)ÃSn(2)ÃCl(3)
Cl(5)ÃSn(2)ÃCl(3)
O(4)ÃSn(2)ÃCl(1)
Cl(5)ÃSn(2)ÃCl(1)
Cl(3)ÃSn(2)ÃCl(1)
O(4)ÃSn(2)ÃCl(4)
Cl(5)ÃSn(2)ÃCl(4)
Cl(3)ÃSn(2)ÃCl(4)
Cl(1)ÃSn(2)ÃCl(4)
O(4)ÃSn(2)ÃCl(2)
Cl(5)ÃSn(2)ÃCl(2)
Cl(3)ÃSn(2)ÃCl(2)
81.65(19)
96.45(19)
175.31(18)
160.57(17)
92.88(15)
90.29(16)
115.74(14)
83.81(13)
93.23(12)
81.89(9)
78.79(14)
94.87(13)
88.93(13)
83.16(9)
164.90(4)
103.4
Ka)ꢃ
/
3.467 mmꢁ1. The data were corrected for Lor-
entz and polarization effects. After refinement with
isotropic displacement parameters for all atoms, an
Table 1
Crystal data and structure refinement for [WH(CO)3(NC-
Me)(PPh3)2][SnCl5×MeOH] (5)
Chemical formula
Molecular weight
Crystal system
C42H38Cl5NO4P2SnW
1162.46
triclinic
¯
P1
Space group
Unit cell dimensions
˚
a (A)
10.166(2)
12.254(2)
18.424(4)
93.31(3)
92.35(3)
94.18(3)
2282.9(8)
2
˚
b (A)
155.3
29.3
˚
c (A)
a (8)
b (8)
g (8)
74.3
114.2
63.2
126.1
3
˚
V (A )
Z
T (K)
57.1
86.7(1)
100
0.10ꢄ0.13ꢄ0.15
1.691
Crystal size (mm)
Dcalc (g cmꢁ3
177.81(9)
94.08(5)
86.74(9)
90.34(5)
95.30(4)
81.66(9)
92.41(5)
96.25(4)
167.91(4)
86.3(1)
)
˚
l (Mo Ka) (A)
m (Mo Ka) (mmꢁ1
F(000)
0.71073
3.467
1136
)
Method of collection
v ꢂ
/
2u scan
2uRange for data collection (8) 6.7B2u B52.0
Index ranges
ꢁ65h 512, ꢁ155k 515,
ꢁ225l 522
8639
7392/511
Number of unique data
Number of data with
[I 52s(I)]
172.84(4)
92.95(5)
Refinement method
Residuals R1, wR2
Full-matrix least-squares on F2
0.0305, 0.0691
1.87/ꢁ1.19
ꢁ3
˚
Final (Dr)(e A
)
Goodness-of-fit on F2
1.063
absorption correction based on the least-squares filled
against jFcjꢁjFoj differences was also applied [39].
Absorption correction factors, 0.726, 1.495
min, max
/

T. Szyman´ska-Buzar et al. / Polyhedron 21 (2002) 1817ꢂ
/
1823
1823
[10] P.K. Baker, S.J. Coles, M.C. Durrant, S.D. Harris, D.L. Hughes,
M.B. Hursthouse, R.L. Richards, J. Chem. Soc., Dalton Trans.
(1996) 4003.
Minimum and maximum value of the absorption
correction factors ranging between 0.726 and 1.495.
Data reduction and analysis were carried out with
Kuma Diffraction (Wroc law) programs. The structure
was solved by heavy-atom methods using the SHELXS-97
program [40] and refined by a full-matrix least-squares
method on all F2 data using the SHELXL-97 program [41]
[11] T. Szyman´ska-Buzar, T. G lowiak, J. Organomet. Chem. 492
(1995) 241.
[12] I. Czelus´niak, T. G lowiak, T. Szyman´ska-Buzar, Inorg. Chem.
Commun. 316 (2000) 285.
[13] D. Miguel, J.A. Pe´rez-Mart´ınez, V. Riera, S. Garcia-Granda,
Polyhedron 14 (1991) 1717.
to R1ꢃ
/
0.0305 and wR2ꢃ0.0691. Non-hydrogen atoms
/
[14] D. Miguel, J.A. Pe´rez-Mart´ınez, V. Riera, S. Garcia-Granda, J.
Organomet. Chem. 455 (1993) 121.
were refined with anisotropic thermal parameters. The
hydrogen atoms were located according to HFIX
procedure using the SHELXL-97 program [41].
[15] F.A. Cotton, J.H. Meadows, Inorg. Chem. 23 (1984) 4688.
[16] B.J. Brisdon, A.G. Hodson, Inorg. Chim. Acta 128 (1987) 51.
[17] T. Szyman´ska-Buzar, T. G lowiak, Polyhedron 16 (1997) 1599.
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2296.
4. Supplementary material
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[21] S.G. Slater, R. Lusk, B.F. Schumann, M. Darensbourg, Organo-
metallics 1 (1982) 1662.
Crystallographic data have been deposited at the
Cambridge Crystallographic Data Centre with deposi-
tion no. 174363. Copies of this information may be
obtained free of charge from The Director, CCDC, 12
[22] V. Zannotti, V. Rutar, R.J. Angelici, J. Organomet. Chem. 414
(1991) 177.
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Inorg. Chim. Acta 259 (1997) 317.
Union Road, Cambridge CB2 1EZ UK (fax: ꢀ44-1223-
/
336033; e-mail: deposit@ccdc.cam.ac.uk or www: http://
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(1988) 1.
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Acknowledgements
Financial support from the Polish State Committee
for Scientific Research (grant No. 3 T09A 059 17) is
gratefully acknowledged. The authors thank to A.
Gadek for synthesis and M. Kowalska and S. Baczyn´ski
˛
for recording the NMR spectra.
[30] W.L. Olson, D.A. Nagaki, L.F. Dahl, Organometallics 5 (1986)
630.
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¨ ¨