Formation of the salt-like complexes [Co{S2CC(PPh 3)2}3][Co(CO)4]3 and [(CO)4Mn{S2CC(PPh3)2}][Mn(CO) 5] from the reaction of the related carbonyl compounds with S 2CC(PPh3)2

Article abstract of DOI:10.1002/zaac.200600116

The betain-like compound S₂CC(PPh₃)₂ (1), which is obtained from CS₂ and the double ylide C(PPh ₃)₂, reacts with [Co₂(CO)₈] and [Mn₂(CO)₁₀] in THF to afford the salt-like complexes [Co{S₂CC(PPh₃)₂}₃][Co(CO) ₄]₃ (2) and [(CO)₄Mn{S₂CC(PPh ₃)₂}][Mn(CO)₅] (3), respectively, in good yields. At both d⁶ cations 1 acts as a chelating ligand. Disproportionation reactions from formal Co⁰ into Co^III and Co^-1 and from Mn⁰ into Mn¹ and Mn ^-1 occurred with the removal of four or one carbonyl groups, respectively. The crystal structures of 2·5.5THF and 3·2THF are reported, which show a shortening of the C-C bond in the ligand upon complex formation. The compounds are further characterized by ³¹P NMR and IR spectroscopy.

Full text of DOI:10.1002/zaac.200600116

DOI: 10.1002/zaac.200600116
Formation of the Salt-like Complexes [Co{S2CC(PPh3)2}3][Co(CO)4]3 and
[(CO)4Mn{S2CC(PPh3)2}][Mn(CO)5] from the Reaction of the Related
Carbonyl Compounds with S2CC(PPh3)2
Wolfgang Petz*, Bernhard Neumüller*, and Judith Hehl
Marburg, Fachbereich Chemie der Philipps-Universität
Received April 20th, 2006.
Abstract. The betain-like compound S2CC(PPh3)2 (1), which is
obtained from CS2 and the double ylide C(PPh3)2, reacts with
[Co2(CO)8] and [Mn2(CO)10] in THF to afford the salt-like
carbonyl groups, respectively. The crystal structures of 2·5.5THF
and 3·2THF are reported, which show a shortening of the CϪC
bond in the ligand upon complex formation. The compounds are
further characterized by 31P NMR and IR spectroscopy.
complexes
[Co{S2CC(PPh3)2}3][Co(CO)4]3
(2)
and
[(CO)4Mn{S2CC(PPh3)2}][Mn(CO)5] (3), respectively, in good
yields. At both d6 cations 1 acts as a chelating ligand. Disproportio-
nation reactions from formal Co0 into CoIII and CoϪI and from
Mn0 into MnI and MnϪI occurred with the removal of four or one
Keywords: Carbodiphosphorane CS2 adduct; Chelating ligand;
Crystal structures; Manganese complex; Cobalt(III) complex
1 Introduction
With silver salts, containing weakly coordinating anions,
interesting coordination compounds with [Agϩ]4 and
[Agϩ]6 cores could be obtained [3]. These results prompted
us to study the coordination chemistry of 1 more intensively
in particular to look at reactions with other transition metal
carbonyl compounds. In this contribution we present the
results of the reaction of 1 with the dinuclear carbonyl com-
plexes [Co2(CO)8] and [Mn2(CO)10].
The betain-like compound S2CC(PPh3)2 (1) is easily
obtained as a bright orange precipitate by adding CS2
to
a
toluene solution of the carbodiphosphorane
Ph3PϭCϭPPh3. Although this adduct has been known
since more than 40 years, the chemistry was only sparingly
explored. At elevated temperature or even upon stirring in
organic solvents at room temperature 1 slowly splits into
SPPh3 and the ylide-like heterocumulene SϭCϭCPPh3 [1].
Recently, we have solved the crystal structure of 1, which
shows a short carbon carbon bond distance and a small
dihedral angle between the CS2 and the CP2 plane of about
20° indicating some double bond character between the
carbon atoms [2]. DFT calculations demonstrated that
Ph3PϭCϭPPh3 mainly acts as a σ-donor via the sp2 carbon
atom but a weak additional π-interaction between the filled
p orbital of the ylidic carbon atom and the empty p orbital
of the CS2 moiety is operative [2]. This electron flow should
also influence the electron density at the sulfur atoms with
result of enhanced nucleophilic properties relative to those
of similar S2CǟD compounds, in which D acts only as a
σ-donor. Further we could show that 1 can act as a biden-
tate ligand towards group 6 carbonyl compounds to pro-
duce the related [(CO)4M{S2CC(PPh3)2}] complexes [2].
2 Results and Discussion
The reactions of 1 with the carbonyl compounds were car-
ried out as heterogeneous reactions in THF, in which 1 is
insoluble. In halogenated hydrocarbons 1 is soluble, but side
reactions with the solvent may occur. If a slight excess
[Co2(CO)8] was slowly added to a suspension of 1 in THF
immediately CO evolution was observed with formation of
a dark red brown solution. After about 10 min CO evol-
ution had ceased and all material was dissolved. The 31P
NMR spectrum of the solution showed one signal at
16.10 ppm. From the THF solution dark red crystals sepa-
rated after several days, which were identified as the salt-
like
complex
[Co{S2CC(PPh3)2}3][Co(CO)4]3·5.5THF
(2·5.5THF). The ligand had induced a disproportionation
reaction from formal Co0 in [Co2(CO)8] into CoIII and
CoϪI in cation and anion, respectively, according to equ.
(1). During the related reaction of a 1 : 2 mixture of 1 with
[Mn2(CO)10] in THF no visible CO evolution was observed.
But after about 10 to 15 h at room temperature all of the
starting betain 1 had dissolved to produce an orange solu-
tion from which the salt-like complex 3 could be isolated
(equ. (2)). The 31P NMR spectrum of the solution gave a
* 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, neumuell@chemie.uni-mar-
burg.de
2232
 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2006, 632, 2232Ϫ2237

[(CO)4Mn{S2CC(PPh3)2}][Mn(CO)5]
signal at 16.6 ppm, which was accompanied by two low in-
tense signals at 42.1 and Ϫ10.2 ppm belonging to SPPh3
and the heterocummulene SϭCϭCϭPPh3, respectively, ac-
cording to a slow decomposition of 1 in solution. Experi-
ments with a 2 : 1 mixture of 1 with [Mn2(CO)10] in THF
gave similar results, but the signals of the decomposition
products of 1 increased. Similar to the formation of 2 a
dismutation occurred starting from Mn0 into MnI and
MnϪI as shown in equ. (2). Parallel to the formation of 3,
in all cases a slow decomposition of 1 is operative according
to equ. (3).
of the [Co(CO)4]Ϫ anion [10, 11]. Further strong bands at
1063 and 1098 belong to the vibration of the CS2 group;
similar bands were recorded in all known complexes with 1
as ligand, and no dependence of the position from charge
and number of the ligands is detectable. The IR spectrum
of 3 in the ν(CO) region is composed of the vibrations of
the terminal CO groups of anion and cation, but which are
clearly separated. For the cation three bands were recorded
at 2086, 2009 (broad with a shoulder), and 1943 cmϪ1 con-
sistent with a local C2v symmetry (2 A1, B1, B2), and this
band pattern is closely related to that of the neutral com-
plexes [(CO)4M{S2CC(PPh3)2}], however, according to the
positive charge, the bands are shifted by about 100 to 145
wave numbers to higher frequencies. Thus, the positive
charge overcompensates the normal low frequency shift of
the chelating ligand, which shows a greater σ-donor/π-ac-
ceptor ratio than CO and which should induce enhanced
back bonding into CO π* orbitals. A similar band pattern
is recorded in the cation [(CO)4Mn{S2CP(C6H11)3}]ϩ [12].
The low frequency bands at 1852, 1884, and 1900 can be
assigned to the CO groups of the anion (A2Љ, EЈ) and are
identical with those in other complexes containing the
[Mn(CO)5]Ϫ anion [13]; the presence of three CO bands
represents the deviation from the ideal D3h symmetry. Two
medium to strong bands at 1066 and 1099 cmϪ1 can be as-
signed to the vibration of the CS2 moiety. 3 does not react
with PPh3 at room temperature even under ultrasonic ir-
radiation; the 31P NMR spectrum of the reaction mixture
shows the unchanged signals of the starting materials.
2 [Co2(CO)8] ϩ 3 S2CC(PPh3)2 Ǟ
[Co{S2CC(PPh3)2}3][Co(CO)4]3 ϩ 4 CO (1)
2
[Mn2(CO)10] ϩ S2CC(PPh3)2 Ǟ
[(CO)4Mn{S2CC(PPh3)2}][Mn(CO)5] ϩ CO (2)
3
S2CC(PPh3)2 Ǟ SPPh3 ϩ SϭCϭCϭPPh3
(3)
The cation of 3 is isoelectronic to the neutral compounds
[(CO)4M{S2CC(PPh3)2}] (M ϭ Cr, Mo, W) published ear-
lier and, similar to these complexes, the cations of 2 and 3
have low spin d6 electron configurations. The replacement
of CO groups by the chelating ligand 1 at one Co atom
caused a heterolytic splitting of the CoϪCo bond [4] with
formation of the stable [Co(CO)4]Ϫ anion and concen-
tration of the ligand at the other cobalt atom, a route which
is typical for the interaction of [Co2(CO)8] with various
Lewis bases. However, the formation of a CoIII cation is
very unusual and disproportionation of [Co2(CO)8] with
soft Lewis bases normally proceeds with the formation of
[CoI][Co(CO)4] compounds while hard O and N donors
favor disproportionation into paramagnetic [CoII][Co(CO)4]2
complexes [5]. To our knowledge, no further reactions of
[Co2(CO)8] with chelating neutral sulfur containing ligands
like 1 are described.
3 Crystal Structures
In order to get a deeper inside into the properties of 2 and
3, the molecular structures were determined by single
crystal X-ray diffraction measurements. Dark red crystals
of [Co{S2CC(PPh3)2}3][Co(CO)4]3·5.5THF (2·5.5THF)
were obtained on standing a THF solution at room
temperature for several days. One anion is disordered in
two
positions
(0.8:0.2).
Orange
crystals
of
The σ-donor/π-acceptor ratio of 1 is greater than that of
CO as shown from IR data of the [(CO)4M{S2CC(PPh3)2}]
complexes (M ϭ Cr, Mo, W) [2], and the ligand favors dis-
proportion over formation of a bridging ligand in a Co2
moiety. To our knowledge, the salt 2 is the first compound
containing a highly charged cation with a CoS6 core and is
also the first one in which more than one of the betain-like
ligand 1 is coordinated at a transition metal atom. Other
CoIII complexes with six sulfur atoms in an octahedral en-
vironment are known with negatively charged dithiocarbox-
ylato [6], dithiocarbamato [7], thioxanthato [8], or xanthato
[9] ligands to produce neutral complexes in all cases, and
starting materials were CoII or CoIII complexes. A hetero-
lytic splitting of the metal metal bond is also operative with
[Mn2(CO)10] to produce the d8 anion [Mn(CO)5]Ϫ and the
d6 cation [Mn(CO)5]ϩ, and the latter is stabilized by re-
placement of only one CO ligand by the chelating ligand 1.
The IR spectrum of 2 exhibits a strong band at
1882 cmϪ1 according to the IR active F2 ν(CO) vibration
[(CO)4Mn{S2CC(PPh3)2}][Mn(CO)5]·2THF
(3·2THF)
formed from a THF solution by layering with n-pentane.
The THF molecules are disordered and could be refined in
two split positions (0.6:0.4). An ORTEP view of the cation
of 2·5.5THF is shown in Figure 1; the Co(S2CCP2)3 core is
separately depicted in Figure 2. The cation of 3·2THF is
shown in Figure 3. Details of the structure determination
are summarized in Table 1; bond distances and angles of
the cations are given in Table 2 and 3. Molecular structures
of similar compounds with the CoS6 core with negatively
charged ligands have been determined earlier [7Ϫ9].
3.1 Molecular structure of 2·5.5THF
The structure shows separated cations and anions with no
remarkable interionic contacts. In the cation the cobalt
atom is surrounded by six sulfur atoms in a distorted octa-
hedral environment. The structure of the cation is depicted
Z. Anorg. Allg. Chem. 2006, 2232Ϫ2237
 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
2233

W. Petz, B. Neumüller, J. Hehl
Table 1 Crystal data and structural refinement details
2·5.5THF
3·2THF
formula
C148H134Co4O17.5P6S6
2806.59
1417.7(1)
4255.7(2)
2369.3(1)
90
C55H46Mn2O11P2S
1118.90
1061.6(1)
1193.9(1)
2174.2(2)
76.11(1)
mw/g·molϪ1
a/pm
b/pm
c/pm
α /°
β /°
102.94(1)
90
84.17(1)
85.44(1)
γ /°
crystal size/mm
volume/pm3·106
Z
0.23ϫ0.2ϫ0.19
13932(1)
4
0.26ϫ0.25ϫ0.16
2656.9(4)
2
dcalc /g·cmϪ3
crystal system
space group
diffractometer
Radiation
temperature/K
µ /cmϪ1
1.338
1.399
monoclinic
P21/c (Nr. 14)
IPDS II (Stoe)
Mo-Kα
193
6.9
triclinic
¯
P1 (Nr. 2)
IPDS II (Stoe)
Mo-Kα
193
6.7
52.49
Ϫ13 Յ h Յ 13
Ϫ14 Յ k Յ 14
Ϫ26 Յ l Յ 26
38734
10639 (0.0607)
6421
Fig.
1
Molecular structure of the cation of [Co{S2CC-
(PPh3)2}3][Co(CO)4]3·5.5THF (2·5.5THF) showing the atom num-
bering scheme. The ellipsoids are drawn at a 40% probability level;
the H atoms at the phenyl groups are omitted for clarity.
2θmax /°
index range
52.41
Ϫ17 Յ h Յ 17
Ϫ51 Յ k Յ 52
Ϫ26 Յ l Յ 29
70156
number of rflns collected
number of indep. rflns (Rint) 24844 (0.0597)
Table 2 Selected bond lengths/pm and angles/°
in the cation of 2
number of observed rflns
with F0 > 4σ(F0)
parameters
absorption correction
structure solution
14207
1561
numerical
direct methods
SHELXS-97 [22]
SHELXH-97 [24]
calculated positions with calculated positions with
common displacement
parameter
0.0597
0.171
615
numerical
Patterson method
SHELXTL-Plus [23]
SHELXL-97 [25]
Co(1)ϪS(1)
Co(1)ϪS(3)
Co(1)ϪS(5)
S(1)ϪC(2)
S(3)ϪC(40)
S(5)ϪC(78)
P(1)ϪC(1)
P(2)ϪC(1)
P(5)ϪC(77)
C(1)ϪC(2)
C(77)ϪC(78)
227.6(1)
227.4(1)
225.4(1)
171.7(4)
171.0(4)
170.0(4)
174.7(5)
176.1(5)
175.7(5)
144.8(6)
145.0(5)
Co(1)ϪS(2)
Co(1)ϪS(4)
Co(1)ϪS(6)
S(2)ϪC(2)
S(4)ϪC(40)
S(6)ϪC(78)
P(3)ϪC(39)
P(4)ϪC(39)
P(6)ϪC(77)
C(39)ϪC(40)
225.0(1)
226.5(1)
226.4(1)
168.9(5)
169.6(5)
170.6(4)
175.2(5)
176.0(5)
174.8(4)
144.0(7)
refinement against F2
H atoms
common displacement
parameter
0.0451
0.1156
0.61
R1
wR2 (all data)
max. electron density left/
(e·pmϪ3)·10Ϫ6
0.75
S(1)ϪCo(1)ϪS(2)
S(1)ϪCo(1)ϪS(4)
S(1)ϪCo(1)ϪS(6)
S(2)ϪCo(1)ϪS(4)
S(2)ϪCo(1)ϪS(6)
S(3)ϪCo(1)ϪS(5)
S(4)ϪCo(1)ϪS(5)
S(5)ϪCo(1)ϪS(6)
Co(1)ϪS(2)ϪC(2)
Co(1)ϪS(4)ϪC(40)
Co(1)ϪS(6)ϪC(78)
P(1)ϪC(1)ϪC(2)
S(1)ϪC(2)ϪS(2)
S(2)ϪC(2)ϪC(1)
S(3)ϪC(40)ϪC(39)
S(3)ϪC(40)ϪS(4)
S(4)ϪC(40)ϪC(39)
P(5)ϪC(77)ϪC(78)
S(5)ϪC(78)ϪS(6)
S(6)ϪC(78)ϪC(77)
75.83(5)
95.10(5)
95.11(5)
93.31(4)
96.09(5)
94.71(5)
95.75(5)
76.10(4)
88.1(2)
S(1)ϪCo(1)ϪS(3)
S(1)ϪCo(1)ϪS(5)
S(2)ϪCo(1)ϪS(3)
S(2)ϪCo(1)ϪS(5)
S(3)ϪCo(1)ϪS(4)
S(3)ϪCo(1)ϪS(6)
S(4)ϪCo(1)ϪS(6)
Co(1)ϪS(1)ϪC(2)
Co(1)ϪS(3)ϪC(40)
Co(1)ϪS(5)ϪC(78)
P(1)ϪC(1)ϪP(2)
P(2)ϪC(1)ϪC(2)
S(1)ϪC(2)ϪC(1)
P(3)ϪC(39)ϪP(4)
P(4)ϪC(39)ϪC(40)
S(3)ϪC(40)ϪC(39)
P(5)ϪC(77)ϪP(6)
P(6)ϪC(77)ϪC(78)
S(5)ϪC(78)ϪC(77)
166.54(4)
95.99(5)
94.66(5)
168.32(5)
75.70(5)
95.36(5)
167.54(5)
86.6(2)
in Figure 1; the Co(S2CCP2)3 core is shown in Figure 2.
Relative to the starting ligand 1 the dihedral angles S2C/
P2C have increased from 20° up to values of 28°, 30°, and
32°; the slightly different angles are probably due to pack-
ing effects. Another important change in going from the
free ligand to the complex is the shortening of the CϪC
distance from 147 pm to about 144.5 pm, indicating a
further increase of the double bond character. Both trends,
CϪC bond shortening and increase of the dihedral angle,
86.9(2)
87.3(2)
87.6(2)
86.9(2)
126.7(2)
115.1(3)
125.2(4)
124.6(3)
117.4(4)
124.5(4)
126.8(2)
116.4(3)
125.3(3)
118.0(3)
109.5(2)
125.3(3)
118.0(3)
109.7(3)
125.7(3)
116.7(3)
109.7(2)
125.0(3)
were
also
recorded
in
the
corresponding
[(CO)4M{S2CC(PPh3)2}] complexes (M ϭ Cr, Mo, W) and
the latter effect interpreted in terms of an increased steric
interaction of phenyl groups with the sulfur atoms upon
CϪC bond shortening, pushing the sulfur atoms further
out of the favored planar arrangement [2]. The PϪC dis-
tance which amounts to 163.1(3) pm in the carbodiphos-
phorane C(PPh3)2 [14] according to a p-σ* interaction in-
creased in going to 1 (175.1(2) pm) and shows a mean value
of 175.4(5) pm in the cobalt complex; the average CϪS
bond length amounts to 170.3(4) pm and is slightly longer
than in the free ligand. The small CS2 bite angle of 108° of
the ligand (125° in the free ligand) leads to three small
(average 75.9°) SCoS angles; within each of the three planes
of the octahedron, spanned by four S atoms and the Co
atom, the sum of SCoS angles amounts to 361.2°, indicat-
ing only a small deviation from planarity. Similarly, the
three four-membered CoSCS rings are planar. The PCP
angles were not influenced on complex formation. The
CoϪS distances (average 226.4(1) pm) do not differ from
those containing CoIII and negatively charged [S2CNR2]Ϫ
ligands [15]. The parameters of the three [Co(CO)4]Ϫ anions
are normal and do not deviate markedly from a tetrahedral
arrangement of the carbonyl groups.
2234
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 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2006, 2232Ϫ2237

[(CO)4Mn{S2CC(PPh3)2}][Mn(CO)5]
Table 3 Selected bond lengths/pm and angles/° in the cation of 3
Mn(1)ϪS(1)
Mn(1)ϪC(1)
Mn(1)ϪC(3)
S(1)ϪC(6)
P(1)ϪC(5)
P(1)ϪC(18)
P(2)ϪC(5)
P(2)ϪC(36)
O(1)ϪC(1)
O(3)ϪC(3)
C(5)ϪC(6)
236.5(1)
181.2(4)
185.4(4)
170.9(3)
176.2(3)
180.9(3)
176.0(3)
180.6(3)
114.7(4)
113.8(4)
143.1(4)
Mn(1)ϪS(2)
Mn(1)ϪC(2)
Mn(1)ϪC(4)
S(2)ϪC(6)
P(1)ϪC(12)
P(1)ϪC(24)
P(2)ϪC(30)
P(2)ϪC(42)
O(2)ϪC(2)
O(4)ϪC(4)
238.5(1)
182.2(4)
186.5(4)
170.4(3)
180.4(3)
181.1(3)
180.4(3)
180.2(3)
113.8(4)
113.4(4)
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(6)
Mn(1)ϪC(2)ϪO(2)
Mn(1)ϪC(4)ϪO(4)
P(1)ϪC(5)ϪC(6)
S(1)ϪC(6)ϪS(2)
72.59(3)
169.4(1)
88.1(1)
96.9(1)
88.4(1)
90.1(2)
92.1(2)
176.0(2)
88.0(1)
179.6(4)
179.2(3)
117.3(2)
110.9(2)
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)
Mn(1)ϪS(1)ϪC(6)
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)
S(2)ϪC(6)ϪC(5)
95.5(1)
88.2(1)
168.1(1)
89.1(1)
95.1(1)
91.3(2)
88.5(1)
178.3(4)
179.1(3)
126.4(2)
116.2(2)
123.9(2)
125.1(2)
Fig. 2 View of the Co(S2CCP2)3 core of 2·5.5THF showing the
atom numbering scheme. The ellipsoids are drawn at a 40 % proba-
bility level.
The SCS angle is slightly more acute, while the SMnS angle
is larger than the related SMS angles (M ϭ Cr, Mo, W).
The dihedral angle between the S2C and the P2C planes
amounts to 29°, which is identical with the related angles
in the neutral group 6 derivatives. The anion has a distorted
trigonal bipyramidal structure with C-Mn-C angles in the
equatorial plane of 124.3(2)°, 120.7(2)° and 115.0(2)°;
the axial CO groups form an angle of 174.9(2)°. The
other C-M-C angles are in the range between 86.6(2)°
and 92.5(2)°. The parameters are similar as in
[C(NMe2)3][Mn(CO)5] reported earlier [13].
3.2 Molecular structure of 3·2THF
No nearer contacts between cation and anion exist. The
structure of the cation is closely related to the structures of
the neutral derivatives of the group 6 transition metal car-
bonyl compounds [(CO)4M{S2CC(PPh3)2}] and is shown in
Figure 3. The two sulfur atoms of the ligand 1 and four CO
groups form a distorted octahedral environment of the MnI
atom. The positive charge has no dramatic influence on the
parameters of the ligand, which are close together within
the group 6 metal complexes. Only the CϪC distance de-
creased by about 2 pm to 143.1(4) pm, while the CϪP dis-
tances increased by about 1 pm to 176.2(2) pm relative to
the neutral species, indicative for a shift of the electron den-
sity away from P to the S atoms upon complex formation.
4 Concluding Remarks
Towards various transition metal complexes the betain 1
acts as a chelating ligand rather than as a monodentate one.
The cobalt complex 2 represents the first compound with a
Fig. 3 Molecular structure of the cation of 3·2THF 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.
Z. Anorg. Allg. Chem. 2006, 2232Ϫ2237
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2235

W. Petz, B. Neumüller, J. Hehl
805 w, 746 m, 720 m, 683 s, 658 s, 626 m, 619 m, 583 w, 556 w,
524 w, 503 w, 497 w, 463 w, 439 w, 412 w.
cationic CoS6 core with a charge of ϩIII and, to our knowl-
edge, 3 is one of the rare examples of a cationic carbonyl
species with the [(CO)4MnS2]ϩ core characterized by X-ray
analysis. Only two further examples were published con-
taining either the S2CPCy3 group [16] or two tetrameth-
ylthiourea molecules [17], respectively. The structures of
various neutral species are also reported containing differ-
ent ligands such as dithioacetato, thiolato, disulfido or
phosphinodithiolato ligands, and in all cases a cis arrange-
ment is realized [18]. Also a variety of structures with neu-
tral [X(CO)3Mn(S2CϪD)] compounds were published [12,
19, 20]. As yet, the group 6 carbonyls and 2 and 3 are the
only carbonyl derivatives containing 1 as chelating ligand.
Our attempts to obtain similar complexes from group 8
transition metal carbonyls have failed and the reaction with
[Ni(CO)4] produced only an oily material which could not
be crystallized as yet. Further studies about the complex
ability of 1 and related compounds are in progress.
Crystallographic data for the structures have been deposited with
the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB21EZ. Copies of the data can be obtained on
quoting the depository numbers CCDC 601918 (2·5.5THF),
CCDC 601919 (3·2THF), (Fax: (ϩ44)1223-336-033; E-mail:
deposit@ccdc.cam.ac.uk).
Financial support of this work was provided by the Deutsche
Forschungsgemeinschaft. W. P. thanks the Max-Planck-Society,
Munich, Germany, for supporting this research project.
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5 Experimental Section
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