The ylide adduct SOC2(PPh3)2 as complex ligand. Reaction with [Mn2(CO)10] and InCl3; crystal structures of [(CO)4Mn(SOC2{PPh3} 2)2][Mn

Article abstract of DOI:10.1002/zaac.200700522

The betain-like SOC₂(PPh₃)₂ (1a) reacts with [Mn₂(CO)₁₀] in THF to produce the salt-like complex [(CO)₄Mn(SOC₂{PPh₃}₂) ₂][Mn(CO)₅] (2)

Full text of DOI:10.1002/zaac.200700522

DOI: 10.1002/zaac.200700522
The Ylide Adduct SOC2(PPh3)2 as Complex Ligand. Reaction with
[Mn2(CO)10] and InCl3; Crystal Structures of
[(CO)4Mn(SOC2{PPh3}2)2][Mn(CO)5] and (H2C{PPh3}2)[InCl4]2
Wolfgang Petz*, Meike Fahlbusch, Enrico Gromm, and Bernhard Neumüller*
Marburg, Fachbereich Chemie der Philipps-Universität
Received November 19th, 2007.
Abstract. The betain-like SOC2(PPh3)2 (1a) reacts with
[Mn2(CO)10] in THF to produce the salt-like complex
[(CO)4Mn(SOC2{PPh3}2)2][Mn(CO)5] (2). 1a is bonded via the
sulfur atoms which are arranged in trans position in the octahedral
environment of the manganese atom. With InCl3 from CH2Cl2
solution the addition product [Cl3In(SOC2{PPh3}2)] (3) is obtained
along with the salt (H2C{PPh3}2)[InCl4]2 (4), which is the result
of proton abstraction from the solvent. The crystal structures of
2·0.5THF and 4·CH2Cl2 are reported. The compounds are further
characterized by IR and 31P NMR spectroscopy.
Keywords: Betain-like compounds; Carbodiphosphorane adducts;
Crystal structures; Indium compounds; Manganese carbonyl
complex
1 Introduction
2 Results and Discussion
The betain-like compound SOC2(PPh3)2 (1a) is an adduct
of COS at the carbodiphosphorane C(PPh3)2 and was first
mentioned in 1966 in a short note without further charac-
terization together with the related adducts of CO2 (1b) and
CS2 (1c) [1]. However, the chemistry of these compounds
remained unexplored until recently. X-ray analyses of 1b
and 1c were obtained by us, and attempts were also under-
taken to study their properties as potential ligands towards
main group or transition metal Lewis acids. According to
the soft nature of the sulfur atoms of 1c, transition metal
complexes of the type [(CO)4M(S2C2{PPh3}2)] (M ϭ Cr,
Mo, W) [2] and [(CO)4Mn(S2C2{PPh3}2)]ϩ [3] could be pre-
We could obtain the “mesomeric inner salt” 1a as a color-
less precipitate by bubbling gaseous COS dried over P2O5
into a solution of C(PPh3)2 in toluene. The IR spectrum of
1a exhibits strong bands at 1122 and 1454 cmϪ1 according
to the ν(CS) and ν(CO) vibrations, respectively. 1a is insol-
uble in toluene and THF but dissolves in halogenated hy-
drocarbons and DMSO. A freshly prepared solution of 1a
in CH2Cl2 exhibits a singlet at 11.9 ppm; however, on
standing for several hours it disappears in favor of the sig-
nal of the cation (HC(PPh3)2)ϩ, indicative for the abstrac-
tion of a proton from the solvent. This Hϩ abstraction
should generate either the anion (HCCl2)Ϫ or, after release
of ClϪ, the carbene HCCl. From the remaining solution of
1a in CH2Cl2 we could identify small amounts of trans-
HClCϭCClH by GC/MS experiments, being the dimeriz-
ation product of the postulated carbene; thus, the overall
reaction can be expressed by the equations (1) and (2):
pared in which 1c acts as a chelating ligand. Silver salts
4ϩ
with weakly coordinating anions gave new Ag4
and
6ϩ
Ag6 units which were hold together by several molecules
of 1c [4]. In contrast, the harder oxygen atoms in 1b pre-
destinates this adduct to join to main group fragments, and
complexes could be isolated in which 1b is present as a chel-
ating or a monodentate ligand [5]. But also tungsten car-
bonyl complexes could be prepared in which 1b acts in both
manners [6]. The S and the O atoms in 1a represent soft
and hard sites of the molecule, respectively, and we were
interested to explore which site could be activated if differ-
ent kinds of Lewis acids are offered. Herein we report on
the preparation and some properties of 1a and the outcome
of its reaction with [Mn2(CO)10] and with InCl3.
1a ϩ CH2Cl2 Ǟ (HC{PPh3}2)Cl ϩ COS ϩ “HCCl”
2„HCCl” Ǟ trans-HClCϭCClH
(1)
(2)
Although the cation (HC(PPh3)2)ϩ bears a free pair of
electrons, no addition compound with COS similar to that
with Agϩ is found [7]; however, a further protonation to
give the dication is possible as shown below.
Addition of 1a to a solution of [Mn2(CO)10] in THF
yields a suspension, and after stirring the mixture magneti-
cally for some hours all material has dissolved to give an
orange yellow solution. Layering the solution with n-pen-
tane produced small yellow crystals along with larger pale
orange crystals. Whereas the yellow crystals could not be
identified as yet, the orange ones were found to be the salt-
* Prof. Dr. Wolfgang Petz, *Prof. Dr. Bernhard Neumüller
Fachbereich Chemie der Universität
D-35032 Marburg
Fax: int.-6421/2825653
E-mail: petz@staff.uni-marburg.de
e-mail: neumuell@chemie.uni-marburg.de
682
© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2008, 634, 682Ϫ687

The Ylide Adduct SOC2(PPh3)2 as Complex Ligand
chelating ligand with the indium atom in a trigonal bipyr-
amidal environment similar as in the reaction product of
InCl3 with O2C2(PPh3)2 (1b) as depicted in Scheme 1 [5].
Apparently InCl3 is not “hard” enough to avoid an S
coordination; a chelating effect may also be taken into ac-
count. The majority of crystals of sufficient quality, how-
ever, turned out to be the salt (H2C{PPh3}2)[InCl4]2 (4) as
a result of solvent deprotonation according to equ. (1) but
with formation of the dication. On longer standing of the
solution only crystals of 4·CH2Cl2 could be isolated. Why
the presence of InCl3 favors the formation of the dication
instead of the salt (HC{PPh3}2)[InCl4] is not yet clear. The
signal at 20.2 ppm in the 31P NMR spectrum is due to the
cation of 4 but it is close to that of the monocation
(HC(PPh3)2)ϩ. Addition of (HC(PPh3)2)I to the CH2Cl2
solution of 4 produces a separate signal at 21.1 ppm due to
this cation.
The salt-like compound 4 is one of the rare examples
with the dication (H2C{PPh3}2)2ϩ established by X-ray
analysis [7, 10]; the salt (H2C{PPh3}2)Br2 described earlier
was used as starting material for the preparation of the
carbodiphosphorane C(PPh3)2 [11]. However, none of the
known salts with the dication (H2C{PPh3}2)2ϩ was ob-
tained from double protonation of C(PPh3)2.
Scheme 1
like complex [(CO)4Mn(SOC2{PPh3}2)2][Mn(CO)5] (2) as
depicted in Scheme 1.
The formation of 2 can be explained with a ligand in-
duced heterolytic cleavage of [Mn2(CO)10] in THF into the
cation [Mn(CO)5]ϩ and the anion [Mn(CO)5]Ϫ. The elec-
tron deficient cation is very reactive and gains stability un-
der addition of two molecules of 1a and release of CO. One
can also speculate on a stepwise substitution via the
[(CO)5Mn(SOC2{PPh3}2)]ϩ cation as intermediate and sub-
sequent CO/1a exchange. The 31P NMR spectrum of 2 in
THF or CH2Cl2 exhibits a singlet at 18.0 ppm, thus in-
ducing a low field shift of 1a upon complex formation. The
IR spectrum of 2 in the ν(CO) region is composed of clearly
separated bands of anion and cation. The low frequency
bands at 1854, 1885, and 1902 cmϪ1 can be assigned to the
vibrations of the CO groups of the anion (A2Љ, EЈ); this
band pattern (with splitting of the EЈ mode) is typical for
the anion according to a deviation from the ideal D3h sym-
metry [2, 8]. Further two bands at 1939 and 1973 cmϪ1 be-
long to the vibrations of the four CO groups of the cation.
For a local D4h symmetry only the IR active Eu band is
expected [9] but the ligands 1a apparently cause the de-
generacy to be cancelled. One strong band at 1084 cmϪ1
can be assigned to the ν(CϭS) and a medium strong band
at 1530 cmϪ1 to the ν(CϭO) vibrations of the ligand; the
shift of the ν(CϭO) band to higher frequencies upon com-
plex formation is due to an increase of double bond charac-
ter.
The soft-soft coordination in 2 prompted us to examine
the possibility of a related hard-hard coordination via the
oxygen atom of 1a. For this reason we chose InCl3 as a
Lewis acid and the reaction was performed in CH2Cl2 solu-
tion. Immediately after starting the reaction, the 31P NMR
spectrum showed a signal at 11.7 of unreacted 1a, two in-
tense signals at 20.1 and 20.6 ppm, and two less intense sig-
nals at 20.9 and 21.2 ppm, indicating the formation of dif-
ferent reaction products. After about 2 h an intense singlet
at 20.6 ppm and a less intense one at 20.9 ppm remained in
the 31P NMR spectrum of the clear colorless solution; after
24 h the signal at 20.9 ppm has disappeared. Precipitation
with n-pentane gave a colorless powder. Attempts to grow
crystals for an X-ray analysis produced two sorts of crystals
upon layering a methylene chloride solution with n-pentane.
Some crystals of bad quality turned out to be the addition
compound [Cl3In(SOC2{PPh3}2)] (3), in which 1a acts as a
3 Crystal Structures
To get more insight into the nature of the complexes and
the bonding situation, X-ray analyses of the compounds
were performed. Pale orange crystals of the salt 2·0.5THF
suitable for an X-ray analysis formed upon layering a THF
solution of the reaction mixture at room temperature with
n-pentane. The compound was refined as a racemic twin
with 0.43(3):0.57(3). Colorless crystals of 3 and 4·CH2Cl2
were obtained by layering a CH2Cl2 solution of the reaction
mixture with n-pentane. However, the bad diffraction qual-
ity of the crystals of 3 did not allow to obtain satisfactory
R values and only a low-resolution solution of the structure
could be determined. The crystal structure of the dication
(H2C{PPh3}2)2ϩ was first described as the [FeCl4]Ϫ salt, but
this compound was obtained from interaction of FeCl3 with
PPh3 in CHCl3 solution [10]. The structures of the cation
of 2·0.5THF and of 4·CH2Cl2 are shown in Figure 1 and
2, respectively; crystallographic data are collected in Table
1; distances and angles are summarized in Tables 2 and 3.
3.1 Crystal Structure of 2·0.5THF
The compound 2 represents the first complex with a cat-
ionic (CO)4MnS2 core in which the sulfur atoms are in a
trans arrangement. The cation of the salt-like complex con-
tains two molecules of 1a which coordinate with the sulfur
atoms at the manganese atom in an η1 manner. The manga-
nese atom is in an octahedral environment with a planar
Mn(CO)4 array. The C-Mn-C angles are slightly different
from 90° showing a pair of smaller and a pair of larger
ones. The distances between the manganese atom and the
Z. Anorg. Allg. Chem. 2008, 682Ϫ687
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683

W. Petz, M. Fahlbusch, E. Gromm, B. Neumüller
Table 1 Crystal data and structural refinement details
2·0.5THF
4·CH2Cl2
Formula
mw/g·molϪ1
a/pm
b/pm
c/pm
α/deg
β/deg
γ/deg
C87H64Mn2O11.5P4S2
1591.34
988.0(1)
3101.4(2)
1318.0(1)
90
97.08(1)
90
C38H34Cl10In2P2
1136.81
1124.0(1)
1213.2(2)
1851.4(2)
105.48(1)
106.79(1)
94.96(1)
crystal size/mm
volume/pm3
Z
0.18ϫ0.15ϫ0.07
0.19ϫ0.05ϫ0.05
2292.4(5)
2
4007.8(6)ϫ106
2
dcalc /g·cmϪ3
crystal system
space group
diffractometer
radiation
temp/K
1.319
monoclinic
P21 (Nr. 4)
IPDS II (Stoe)
Mo-Kα
193
5.1
1.647
triclinic
¯
P1 (Nr. 2)
IPDS II (Stoe)
Mo-Kα
100
16.9
μ/cmϪ1
2θmax/deg
index range
52.47
Ϫ12 Յ h Յ 12
Ϫ36 Յ k Յ 38
52.04
Ϫ13 Յ h Յ 13
Ϫ14 Յ k Յ 14
Ϫ14 Յ l Յ 16
30374
Ϫ22 Յ l Յ 22
29110
No. of rflns collected
No. of indep. rflns (Rint
No. of observed rflns with F0 > 4σ(F0)
parameters
)
14102 (0.1088)
7028
944
8921 (0.0812)
4717
478
absorption correction
structure solution
numerical
direct methods SHELXS-97 [18]
SHELXL-97 [19]
calculated positions with common displacement
numerical
direct methods SHELXS-97 [18]
SHELXL-97 [19]
calculated positions with common displacement
refinement against F2
H atoms
parameter
0.0683
0.1512
0.44
parameter. H(1) and H(2) were refined free
R1
0.0368
0.0633
0.58
wR2 (all data)
max. electron density left (e/pm3) ϫ 10Ϫ6
carbonyl carbon atoms range between 181 and 189 pm. The
cation is centrosymmetric (not crystallographically) as de-
picted in Figure 1. The C-C bond lengths in the ligands are
148 and 147 pm, and the dihedral angles SOC/P2C amount
to 18° and 20°, respectively; both parameters are probably
due to a π interaction of the filled p orbital at the PCP
carbon atom with the vacant p orbital of the OCS carbon
atom. The atoms C(6) and C(44) are in a planar environ-
ment with the sum of the angles of 359.8(7)° and 359.9(7)°.
The Mn-S distances are normal as found in other com-
pounds with the (CO)4MnS2 units [12], but shorter than in
compounds with a (CO)5MnS moiety [13]. The two C-S
bond lengths differ by about 5 pm, but are longer than the
mean value of C-S distances of about 170 pm in the free
ligand S2C2(PPh3)2 (1c) and in its (CO)4M complexes (M ϭ
Cr, Mo, W [2], Mnϩ [3]) indicating only a weak double
bond character. In contrast, the uncoordinated C-O bonds
differ by about 4 pm but are closely related to those in the
η1 bonded ligand O2C2(PPh3)2 (1b). It is interesting to see
that in 2 the long C-S bond belongs to the short C-O bond
while the short C-S bond is accompanied by the long C-O
bond. The anion shows a slight disorder but the parameters
are closely related to those in other complexes with this
anion [8].
Fig.
1
Molecular
structure
of
the
cation
of
[(CO)4Mn(SOC2{PPh3}2)2][Mn(CO)5] (2·0.5THF) showing the
atom numbering scheme. The ellipsoids are drawn at a 40 % proba-
bility level; the H atoms at the phenyl rings are omitted for clarity.
3.2 Crystal Structure of 4·CH2Cl2
The molecular structure of 4·CH2Cl2 is shown in Figure 2.
The CH2Cl2 molecules are disordered and not shown. The
P-C-P angle amounts to 123° and is more acute than the
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The Ylide Adduct SOC2(PPh3)2 as Complex Ligand
Table 2 Selected bond lengths/pm and angles/° in the cation of 2
Mn(1)ϪS(1)
Mn(1)ϪC(1)
Mn(1)ϪC(3)
S(1)ϪC(6)
P(1)ϪC(5)
P(2)ϪC(5)
O(1)ϪC(1)
236.8(3)
187 (1)
185 (1)
178.2(9)
175.3(9)
173.3(8)
110(1)
Mn(1)ϪS(2)
Mn(1)ϪC(2)
Mn(1)ϪC(4)
S(2)ϪC(44)
P(3)ϪC(43)
P(4)ϪC(43)
O(2)ϪC(2)
236.4(3)
181 (1)
189(1)
173.4(8)
175.1(8)
175.4(9)
119(1)
O(3)ϪC(3)
O(5)ϪC(6)
112(1)
122(1)
O(4)ϪC(4)
O(6)ϪC(44)
114(1)
126(1)
C(5)ϪC(6)
148(1)
C(43)ϪC(44)
147(1)
S(1)ϪMn(1)ϪS(2)
S(1)ϪMn(1)ϪC(2)
S(1)ϪMn(1)ϪC(4)
S(2)ϪMn(1)ϪC(2)
S(2)ϪMn(1)ϪC(4)
C(1)ϪMn(1)ϪC(3)
C(2)ϪMn(1)ϪC(3)
C(3)ϪMn(1)ϪC(4)
Mn(1)ϪS(2)ϪC(44)
C(5)ϪP(1)ϪC(13)
C(5)ϪP(2)ϪC(31)
C(43)ϪP(3)ϪC(51)
C(43)ϪP(3)ϪC(57)
C(43)ϪP(4)ϪC(63)
C(43)ϪP(4)ϪC(75)
Mn(1)ϪC(2)ϪO(2)
Mn(1)ϪC(4)ϪO(4)
P(1)ϪC(5)ϪC(6)
S(1)ϪC(6)ϪO(5)
O(5)ϪC(6)ϪC(5)
P(3)ϪC(43)ϪC(44)
S(2)ϪC(44)ϪO(6)
O(6)ϪC(44)ϪC(43)
179.6(1)
90.0(3)
94.9(3)
90.1(3)
84.7(3)
87.0(4)
91.0(5)
179.6(4)
110.0(3)
115.1(4)
114.1(4)
114.7(4)
113.9(4)
114.7(4)
113.9(4)
176.3(9)
174.3(8)
119.4(6)
122.6(7)
121.2(8)
111.0(6)
123.0(7)
118.7(7)
S(1)ϪMn(1)ϪC(1)
S(1)ϪMn(1)ϪC(3)
S(2)ϪMn(1)ϪC(1)
S(2)ϪMn(1)ϪC(3)
C(1)ϪMn(1)ϪC(2)
C(1)ϪMn(1)ϪC(4)
C(2)ϪMn(1)ϪC(4)
Mn(1)ϪS(1)ϪC(6)
C(5)ϪP(1)ϪC(7)
C(5)ϪP(1)ϪC(19)
C(5)ϪP(2)ϪC(25)
C(5)ϪP(2)ϪC(37)
C(43)ϪP(3)ϪC(45)
C(43)ϪP(4)ϪC(69)
Mn(1)ϪC(1)ϪO(1)
Mn(1)ϪC(3)ϪO(3)
P(1)ϪC(5)ϪP(2)
P(2)ϪC(5)ϪC(6)
S(1)ϪC(6)ϪC(5)
P(3)ϪC(43)ϪP(4)
P(4)ϪC(43)ϪC(44)
S(2)ϪC(44)ϪC(43)
90.8(3)
85.3(3)
89.0(3)
95.1(3)
177.7(5)
93.4(4)
88.7(4)
108.6(3)
111.6(4)
112.4(4)
115.7(4)
108.5(4)
108.0(4)
104.9(4)
178.1(9)
174.0(8)
130.6(5)
109.8(6)
116.0(6)
130.6(5)
118.4(6)
118.2(6)
Fig. 2 Molecular structure of (H2C{PPh3}2)[InCl4]2 (4·CH2Cl2)
showing the atom numbering scheme. The ellipsoids are drawn at
a 40 % probability level; the H atoms at the phenyl rings are
omitted for clarity.
Table 3 Selected bond lengths/pm and angles/° in 4·CH2Cl2
P(1)ϪC(1)
P(1)ϪC(8)
P(2)ϪC(1)
P(2)ϪC(26)
C(1)ϪH(1)
In(1)ϪCl(1)
In(1)ϪCl(3)
In(2)ϪCl(5)
182.5(5)
179.1(4)
182.5(5)
178.3(4)
97(3)
236.5(2)
232.8(2)
236.2(1)
234.0(2)
110.0(2)
109.5(2)
106.1(2)
123.1(3)
104(2)
P(1)ϪC(2)
P(1)ϪC(14)
P(2)ϪC(20)
P(2)ϪC(32)
C(1)ϪH(2)
In(1)ϪCl(2)
In(1)ϪCl(4)
In(2)ϪCl(5)
178.5(5)
179.3(5)
179.1(5)
179.9(5)
92(4)
232.8(1)
235.3(2)
233.5(1)
234.3(2)
110.9(2)
110.6 (2)
110.8(2)
108(2)
related angle in (HC{PPh3}2)ϩ (130°). The carbon atom of
the CH2 group is in a distorted tetrahedral environment
with an approximate sp3 hybridization and the deviation of
the P-C-P angle from a normal tetrahedral angle presum-
ably is a result of the bulkiness of the PPh3 groups. Each
H atom forms a weak H bridge to an [InCl4]Ϫ anion with
C(1)····Cl distances of 360 and 403 pm to Cl(5) and Cl(4),
respectively. The C-H distances in the CH2 group are signif-
icantly longer than the C-H distance in the monocation
(HC{PPh3}2)ϩ. The P-C bond lengths to C(1) are very long
(182.5(5) ppm) but they are in the expected range for an sp3
carbon atom in a P-C single bond; shorter bond lengths are
found in the monocation (169.9(2) pm) and in the carbodi-
phosphorane (163.5(5) pm); these bond shortenings are due
to a partial back bonding of the occupied p orbitals at the
carbon atom into σ* P-Cphenyl orbitals. The [InCl4]Ϫ anions
display fairly regular tetrahedrons. The In-Cl bond lengths
vary between 232.8(2) and 236.5(2) pm (average
234.4(2) pm) and can be compared with those found in
other salts containing this anion [14].
In(2)ϪCl(5)
In(2)ϪCl(5)
C(1)ϪP(1)ϪC(2)
C(1)ϪP(1)ϪC(14)
C(1)ϪP(2)ϪC(20)
P(1)ϪC(1)ϪP(2)
P(1)ϪC(1)ϪH(1)
P(2)ϪC(1)ϪH(2)
Cl(1)ϪIn(1)ϪCl(2)
Cl(1)ϪIn(1)ϪCl(4)
Cl(2)ϪIn(1)ϪCl(4)
Cl(5)ϪIn(2)ϪCl(6)
Cl(5)ϪIn(2)ϪCl(8)
Cl(6)ϪIn(2)ϪCl(8)
C(1)ϪP(1)ϪC(8)
C(1)ϪP(2)ϪC(26)
C(1)ϪP(2)ϪC(32)
P(1)ϪC(1)ϪH(1)
P(2)ϪC(1)ϪH(1)
H(1)ϪC(1)ϪH(2)
Cl(1)ϪIn(1)ϪCl(3)
Cl(2)ϪIn(1)ϪCl(3)
Cl(3)ϪIn(1)ϪCl(4)
Cl(5)ϪIn(2)ϪCl(7)
Cl(6)ϪIn(2)ϪCl(7)
Cl(7)ϪIn(2)ϪCl(8)
105(2)
110(3)
105(2)
111.97(6)
105.94(6)
110.91(6)
111.36(5)
107.72(6)
108.65(5)
111.92(6)
110.66(6)
105.12(8)
108.59(6)
109.62(6)
112.87(7)
[4]. From earlier results we know that 1b in the presence of
Lewis acids form either complexes or deprotonate solvents
like dichloromethane or even THF more quickly with result
of the cations (HC{PPh3}2)ϩ or (H2C{PPh3}2)2ϩ [15]. As
yet, we are not able to predict what cation will be formed,
and the outcome probably depends on the nature of the
solvent and the Lewis acid attached. The formation of the
compounds 2, 3 and 4 as well as the reaction with CH2Cl2
demonstrates that 1a acts in the same manner.
4 Conclusion
The hexaphenylcarbodiphosphorane adduct 1a is soluble in
CH2Cl2 but reacts slowly with the solvent to give the cation
(HC{PPh3}2)ϩ. This is also the case for the related CO2
adduct 1b and both are able to act as monodentate or bi-
dentate ligand. However, the related CS2 adduct 1c was
only observed in an η2 bonding manner to transition metals
Unfortunately we could not obtain the crystal structures
of the potential O,S ligand 1a or of 3 as yet in order to
compare the parameters of 1a in different bonding modes.
Z. Anorg. Allg. Chem. 2008, 682Ϫ687
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W. Petz, M. Fahlbusch, E. Gromm, B. Neumüller
magnetically for about 48 h. The resulting orange solution was fil-
tered from small amounts of an insoluble material and layered with
n-pentane. After 2 days orange crystals have separated along with
some small yellow crystals. The orange crystals were separated and
identified as 2·0.5THF. 31P NMR (CH2Cl2): s, 18.0 ppm. IR (Nu-
jol mull, cmϪ1): 1973 s, 1939 s, 1902 s, 1885 m, 1854 vs, 1588 w,
1530 m, 1483 m, 1441 s, 1402 w, 1261 w, 1103 vs, 1084 sh, 1028 w,
999 w, 745 m, 719 m, 683 m, 658 w, 650 w, 619 w, 583 w.
However, as reported earlier, data for the related O,O ligand
1b are available. If we compare the C-C bond length
in 1b (149.4(3) pm) with those in the complexes
[(CO)4W{O2C2{PPh3}2] (η2), [(CO)5W{O(O)C2{PPh3}2]
(η1) [6] and [Cl2Sn{O(O)C2{PPh3}2] (η1) [5], amounting to
144.4(9), 147.5(8) and 145.3(8) pm, respectively, it can be
deduced that the double bond character of the C-C bond
in the ligand systems 1b increases in the row 1b < η1-1b <
η2-1b corresponding to an electron release caused by the
Lewis acids which is compensated by a stronger π donation
from the filled p orbital of the ylidic carbon atom to the
empty p orbital of the heteroallene carbon atom. The C-C
bond length in 2 is 148(1) pm and close to the value in
the η1 bonded tungsten complex [(CO)5W{O(O)C2{PPh3}2]
indicating a similar electron release.
The isolation of 2 and 3 demonstrates the ability of 1a to
act as monodentate or chelating ligand, but the question of
donating exclusively with the O-site is still open. Further
studies on the complex chemical properties of 1a are in pro-
gress and concentrate on the choice of suitable hard Lewis
acids and on finding conditions to minimize solvent reac-
tions by sufficient solubility properties.
Reaction of 1a with InCl3: 510 mg of 1a (0.86 mmol) and 190 mg
InCl3 (0.86 mmol) were dissolved in about 20 ml CH2Cl2 at 0 °C
and the mixture was stirred for 20 min. A clear solution was ob-
tained. In the 31P NMR spectrum of the solution after about
20 min two signals at 20.1 and 20.6 ppm were found attributed to
3 and 4, respectively. The mixture was allowed to stand for about
5 h at room temperature. Then it was layered with n-pentane. After
several days crystals separated which consisted mainly of 4. IR
(Nujol mull, cmϪ1): 1481 m, 1439 s, 1337 w, 1316 w, 1265 w, 1169 s,
1103 vs, 1059 m, 1026 w, 997 m, 748 s, 719 m, 714 m, 691 s, 662 w,
592 w, 526 m, 517 s, 507 s.
Crystallographic data for the structures have been deposited with
the Cambridge Crystallographic Data Center, 12 Union Road,
Cambridge CB21EZ. Copies of the data can be obtained on quot-
ing the depository numbers CCDC 651194 (2), and CCDC 612360
(4), (Fax: (ϩ44)1223-336-033; E-mail: deposit@ccdc.cam.ac.uk).
5 Experimental Section
Acknowledgement. We thank the Deutsche Forschungsgemeinschaft
for financial support. We also thank Dr. K. Steinbach for per-
forming the GC/MS experiments. W. P. is also grateful to the Max-
Planck-Society, Munich, Germany, for supporting this research
project.
All operations were carried out under an argon atmosphere in dried
and degassed solvents using Schlenk techniques. The solvents were
thoroughly dried and freshly distilled prior to use. The IR spectra
were run on a Nicolet 510 spectrometer. For the 31P NMR spectra
we used the instrument Bruker AC 200. 1a was prepared according
to a modified literature procedure [1]; COS was obtained as de-
scribed in [16]. Commercially available [Mn2(CO)10] was sublimed
prior to use, and InCl3 was obtained according to literature pro-
cedures from the elements [17].
References
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Chem. Commun. 1966, 736.
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Preparation of SOC2(PPh3)2 (1a): Freshly prepared COS gas was
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[1]. A pale yellow powder of 1a precipitated quantitatively, which
was filtered and dried in vacuo. 1a is insoluble in toluene but dis-
solves in CH2Cl2 or 1,2-dichloroethane under slow decomposition
and formation of the cation (HC{PPh3}2)ϩ. 31P NMR (CH2Cl2):
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1437 s, 1358 w, 1312 w, 1184 w, 1161 w, 1154 w, 1123 vs, 1099 vs,
1026 w, 999 m, 745 m, 718 m, 706 m, 691 s, 588 m, 534 m, 521 s.
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dissolved in 2 mL of CH2Cl2. The 31P NMR spectrum showed
singlets at 11.9 ppm and 20.6 ppm in a 1:0.3 ratio immediately after
dissolving assigned to 1a and the cation (HC{PPh3}2)ϩ, respec-
tively. After about 3 h only the signal of the cation was found. The
solution was allowed to stand for about 10 h; then all volatile mate-
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GC/MS; from MS studies the formation of trans-HClCϭCClH
could be established. If 1a was dissolved in 1,2-dichloroethane solu-
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solution a singlet appeared at 10.0 ppm, which did not change
within 24 h. The compound is insoluble in THF and toluene.
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