Synthesis and reactivity of half-sandwich type cobalt, rhodium and iridium complexes containing trithiocarbonate, dithiocarbonate, N-cyanodithiocarbimate, 1,1-dicyanoethylene-2,2-dithiolate and 1,1-dicyanoethylene-2,2-diselenolate as chelating ligands

Article abstract of DOI:10.1016/j.poly.2011.11.044

A series of half-sandwich type complexes with [(C₅R ₅)Co(L)] (R = H, Me; L = PR₃, P(OR)₃, CNR), [(C₅R₅)RhPR3′] (R = H, Me) and [(C₅H ₅)Ir(PiPr₃)] as building blocks and trithiocarbonate, dithiocarbonate, N-cyanodithiocarbimate, 1,1-dicyanoethylene-2,2-dithiolate and 1,1-dicyanoethylene-2,2-diselenolate as chelating ligands was prepared. They were characterized by mass spectrometry and IR, UV, and NMR spectroscopic techniques. The trithiocarbonate derivatives [(C₅R ₅)Co(PMe₃)(S₂CS)] (R = H, Me) were oxidized with [Fe(C₅H₅)₂]X (X = BF₄, PF ₆) to the cationic compounds [(C₅R₅)Co(PMe ₃)(S₂CS)]X. The oxidation potentials of the half-sandwich type complexes were determined by cyclovoltammetry. The reaction of [(C ₅Me₅)Co(PMe₃)(S₂CS)] with tetracyanoethylene (TCNE) led to a ligand fragment exchange and gave the cobalt 1,1-dicyanoethylene-2,2-dithiolate [(C₅Me₅)Co(PMe ₃){S₂CC(CN)₂}] in good yield.

Full text of DOI:10.1016/j.poly.2011.11.044

Polyhedron 34 (2012) 13–23
Contents lists available at SciVerse ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Synthesis and reactivity of half-sandwich type cobalt, rhodium and iridium
complexes containing trithiocarbonate, dithiocarbonate, N-cyanodithiocarbimate,
1,1-dicyanoethylene-2,2-dithiolate and 1,1-dicyanoethylene-2,2-diselenolate
as chelating ligands
⇑
Helmut Werner , Lothar Scheller
Institut für Anorganische Chemie der Universität Würzburg, Am Hubland, D-97074 Würzburg, Germany
a r t i c l e i n f o
a b s t r a c t
Article history:
A
series of half-sandwich type complexes with [(C5R5)Co(L)] (R = H, Me; L = PR3, P(OR)3, CNR),
[(C5R5)RhPR0 ] (R = H, Me) and [(C5H5)Ir(PiPr3)] as building blocks and trithiocarbonate, dithiocarbonate,
Received 26 October 2011
Accepted 22 November 2011
Available online 1 December 2011
3
N-cyanodithiocarbimate, 1,1-dicyanoethylene-2,2-dithiolate and 1,1-dicyanoethylene-2,2-diselenolate
as chelating ligands was prepared. They were characterized by mass spectrometry and IR, UV, and
NMR spectroscopic techniques. The trithiocarbonate derivatives [(C5R5)Co(PMe3)(S2C@S)] (R = H, Me)
were oxidized with [Fe(C5H5)2]X (X = BF4, PF6) to the cationic compounds [(C5R5)Co(PMe3)(S2C@S)]X.
The oxidation potentials of the half-sandwich type complexes were determined by cyclovoltammetry.
The reaction of [(C5Me5)Co(PMe3)(S2C@S)] with tetracyanoethylene (TCNE) led to a ligand fragment
exchange and gave the cobalt 1,1-dicyanoethylene-2,2-dithiolate [(C5Me5)Co(PMe3){S2C@C(CN)2}] in
good yield.
Dedicated to Professor Malcolm Green
on the occasion of his 75th birthday, to
commemorate the golden years of the
fierce Fischer/Wilkinson competition
Keywords:
Cobalt
Rhodium
Ó 2011 Elsevier Ltd. All rights reserved.
Iridium
Chelate complexes
Cyclovoltammetry
1. Introduction
[(C5Me5)M] other complexes of type A were obtained and investi-
gated for their optical and electrochemical properties [7].
Following our work on half-sandwich type cobalt and rhodium
complexes formed from CS2, CSe2 and related heteroallenes [1,2],
we were interested to find out whether dinuclear compounds of
the general composition [(C5R5)(L)M(S2C@CS2)M(L)(C5R5)] could
be prepared and, if they could, whether they would behave as elec-
tron donor molecules similar to tetrathiofulvalenes [3]. In 2000,
Rauchfuss and co-workers disclosed that the dechlorination of the
The aim of this study was to prepare complexes of type B on a
route as straightforward as possible. In order to reach this goal, we
decided to use trithiocarbonato, dithiocarbonato and N-cya-
nodithiocarbimato complexes containing the molecular unit
[(C5R5)M(L)] (M = Co, Rh, Ir; R = H, Me) as starting materials. By
applying established procedures to convert compounds with the
fragments S2C@S, S2C@O and S2C@NR by methylation to the corre-
sponding cationic species, we hoped that by subsequent abstraction
of SMe, OMe and NR2 the target molecules could be obtained.
tetrathiooxalato complex [{(C5Me5)(Cl)Rh}2(
formation of the ethylenetetrathiolato compound [{(C5Me5)Rh}2-
-C2S4)] of type A (Scheme 1) [4]. Earlier, Dahl and co-workers
described the high-yield synthesis and molecular structure of
[{(C5Me5)Ni}2( -C2S4)], being the first example of a type A complex
l-S2S4)] led to the
(l
l
2. Results and discussion
[5]. More recently, Guyon et al. reported that the reaction of
[(C5Me5)Co(CO)2] with CS2 gave an isomeric mixture of the cobalt
compound [{(C5Me5)Co}2(l-C2S4)] containing both type A and type
B derivatives [6]. In addition, with MLn building blocks other than
The cyclopentadienyl cobalt diiodides 1a, 1f and 1g reacted
with equimolar amounts of K2CS3 in CH2Cl2 at room temperature
to give the corresponding trithiocarbonates 4a, 4f and 4g in good
yields (Scheme 2). Prior to our work, Manning and co-workers pre-
pared the analogues 4b–4e on a similar route [8]. In contrast to
Manning’s synthetic protocol, we found that K2CS3 is more favour-
able than Na2CS3 as the precursor for the trithiocarbonato ligand
because it is less sensitive to hydrolysis.
⇑
Corresponding author. Tel.: +49 931 31 85270; fax: +49 931 84623.
E-mail address: helmut.werner@mail.uni-wuerzburg.de (H. Werner).
0277-5387/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2011.11.044

14
H. Werner, L. Scheller / Polyhedron 34 (2012) 13–23
S
S
S
S
S
S
S
LnM
MLn
P(OEt)3
excess
LnM
MLn
Co
Co
S
S
S
R3P
(EtO)3P
S
S
C
C
type A
type B
S
S
4a, 4b, 4d
4h
Scheme 1.
Scheme 3.
K2CS3
R
R
BF4
Co
Co
R
R
R
R
R
I
S
L
L
I
S
C
R
R
R
S
[OMe3]BF4
Co
Co
S
S
L
L
S
S
1a, 1f, 1g
4a, 4f, 4g
C
C
S
SMe
4a-d, 4f, 4g, 5a-5d
6a-6f, 7a-7d
Me
Me
Me
Me
Me
Me
Me
Me
Me
Me
R
H
H
H
H
H
L
R
H
L
K2CS3
Co
Co
6a
6b
6c
6d
6e
PMe3
6f
I
S
CNPh
R3P
R3P
I
S
C
PMe2Ph
PMePh2
PPh3
Me PMe3
7a
7b
7c
7d
S
Me PMe2Ph
Me PMePh2
Me PPh3
3a-3d
5a-5d
CHMe
L
PR3
Scheme 4.
PMe3
CNMe
CNPh
PMe3
1a, 4a
1f, 4f
1g, 4g
3a, 5a
3b, 5b
3c, 5c
3d, 5d
PMe2Ph
PMePh2
PPh3
Treatment of 5a or 5c with P(OEt)3 (ratio 1:5) in benzene at
40 °C under UV irradiation afforded mixtures of [(C5Me5)-
Co{P(OEt)3}(S2C@S)] and 5a or 5c, which could not be separated
either by fractional crystallization or column chromatography. In
the presence of the distannane Sn2nBu6, which was used by Ueno
et al. for the preparation of a variety of tetrathiofulvalenes from
1,3-dithio-2-thiones probably via 1,3-dithiocarbenes [13], 4b and
4c proved to be inert, even under photochemical conditions. Other
attempts with Co2(CO)8 as sulfur abstracting reagent [14] and
either the cyclopentadienyl or the pentamethylcyclopentadienyl
cobalt trithiocarbonates as precursors also remained unsuccessful.
To find out whether the desired tetrathiofulvalene analogues of
type B were accessible via the methylated derivatives of the cobalt
trithiocarbonates, the two series of compounds 6a–6f and 7a–7d
were prepared (Scheme 4). In contrast to Manning’s and Bianchi-
ni’s work [8,15], we used instead of methyl iodide Meerwein’s re-
agent [OMe3]BF4 as methyl source and, in CH2Cl2 at room
temperature, obtained the tetrafluoroborates 6a–6f and 7a–7d in
80–92% yield. Typical spectroscopic data of the methylthioxanth-
ate complexes are the singlet for the SCH3 protons at d 2.4–2.8 in
the 1H NMR and the C–SCH3 stretching mode at 980–990 cmꢀ1 in
Scheme 2. Complex 4b: [(C5H5)Co(PMe2Ph)(S2C@S)]; 4c: [(C5H5)Co(PMePh2)(S2C@S)];
4d: [(C5H5)Co(PPh3)(S2C@S)]; 4e: [(C5H5)Co{P(OPh)3}(S2C@S)]).
With 3a–3d as starting materials, the pentamethylcyclopenta-
dienyl complexes 5a–5d were obtained (Scheme 2) and, similar
to 4a, 4f, 4g, characterized by elemental analysis and spectroscopic
techniques. The diiodides 3a and 3c were prepared by ligand dis-
placement from [(C5Me5)Co(CO)I2] and PR3 using the synthetic
procedure described by Fairhurst and White [9]. In contrast to
King’s work [10], the triphenylphosphine derivative 3d was ob-
tained as the sole product in high yield from [(C5Me5)CoI2]2 and
PPh3 by cleavage of the iodide bridges. With regard to the IR spec-
tra of 4a, 4f, 4g and 5a–5d we note that neither the ring ligand nor
the phosphine has a significant influence on the frequency of the
C@S stretching mode. The same is true for the band in the UV spec-
tra of 4a and 5a–5d at k 356–362 nm, which is assigned to a
interligand transition of the S2C@S ligand [11].
p ?
p⁄
Attempts to abstract the exocyclic sulfur atom of the MS2C@S
unit in the 4a–4g and the 5a–5d series failed. The reactions of
4a, 4b and 4d with an excess of P(OEt)3 in benzene at room tem-
perature or under reflux only led to a phosphine/phosphite ex-
change and gave the substitution product 4h in moderate to
good yield (Scheme 3). Under similar conditions, tetrathiofulvalene
derivatives were obtained from five-membered 1,3-dithio-
2-thiones and P(OEt)3 [12]. Similar attempts with 4a or 4e and
PnBu3 as starting materials also gave the substitution product
[(C5H5)Co(PnBu3)(S2C@S)], which was already known [8].
the IR spectra. The lowering of the
m(C–SCH3) mode by only ca.
40–50 cmꢀ1 compared with the
m
(C@S) mode in the spectra of
4a, 4f, 4g and 5a–5d indicates that the C–S bond in 6a–6f and
7a–7d retains some double bond character. This is in agreement
with previous results reported by Roper’s group [16] and by others
[17].
Despite the weakening of the C–SCH3 bond in 6a–6f and 7a–7d
compared with the C@S bond in 4a, 4f, 4g and 5a–5d, all attempts
to abstract the SCH3 fragment of the methylthioxanthate ligand
failed. In contrast to studies by Fanghänel et al., which showed that

H. Werner, L. Scheller / Polyhedron 34 (2012) 13–23
15
proposed to be due to Fermi resonance between the carbon–oxy-
gen stretching mode and the first overtone band of the carbon–sul-
fur asymmetric stretching mode [22]. This mode was also observed
in other metal dithiocarbonates [8,23]. From the experiments car-
ried out to abstract the oxygen atom of the S2C@O ligand, mention
should be made of the reactions of 10b and 11a with an excess of
P(OEt)3 or P(OMe)3, which gave the corresponding cobalt deriva-
tives 12 and 13 by phosphine/phosphite exchange. Under similar
conditions, tetrathiofulvalenes were obtained by treatment of
1,3-dithiol-2-ones and P(OEt)3 or P(OMe)3 [12c–f]. Attempts to oxi-
dize 10a and 11a with [Fe(C5H5)2]PF6 in CH2Cl2, similar as carried
out with 4a and 5a to afford 8b and 9b (see Scheme 5), failed. It
should also be noted that the reactions of 10a and 11a with
Meerwein’s reagent [OMe3]BF4 gave a mixture of products, while
treating 10a and 11a with two equivalents of Me3SiCl led to the
displacement of the dithiocarbonate ligand and the formation of
14a [24] and 14b.
R
R
X
R
R
R
R
R
R
[Fe(C5H5)2]X
[Co(C5H5)2]
R
R
Co
Co
S
S
Me3P
Me3P
S
S
C
C
S
S
4a, 5a
8a,b; 9a,b
R
H
H
X
BF4
PF6
8a
8b
9a
9b
Me BF4
Me PF6
Scheme 5.
The X-ray diffraction analysis of 11b confirmed the structural
proposal shown in Scheme 6 [25].1 The planar cyclopentadienyl
ring is slightly unsymmetrically coordinated to the cobalt atom
with Co–C distances lying between 2.063(3) and 2.116(3) Å. The
bond angles between cobalt and the phosphorus and the sulfur
atoms, which occupy the three legs of the pianostool configuration,
are P–Co–S(1) = 93.98(3)°, P–Co–S(2) = 89.01(4)° and S(1)–Co–
S(2) = 77.24(4)°, the latter being determined by the relatively small
bite angle of the dithiocarbonate ligand. The bond lengths Co–
S(1) = 2.241(1) Å and Co–S(2) = 2.252(1) Å are almost identical to
the Co–S bond lengths in [(C5H5)Co(CNtBu)(S2C@S)] (2.235(3)
tetrathiofulvalenes can be prepared on treating 2-alkylthio- or 2-
arylthio-1,3-dithiolium salts with phosphines or phosphites [18],
the cobalt compounds 6a–6f and 7a–7d were inert in the presence
of PMe3, PPh3 and P(OEt)3. Moreover, attempts to cleave the C–
SCH3 bond on a reductive route, as used for the synthesis of tetra-
thiofulvalenes from 2-alkylthio-1,3-dithiolium salts [18,19], re-
mained unsuccessful. Although the reduction potential of the
complexes 6a–6f and 7a–7d, determined by cyclovoltammetry
(see below), indicated that reagents such as [Co(C5H5)2] or Zn [20]
should be suitable to reduce the cationic cobalt methylthioxanth-
ates, we observed only decomposition by reacting 6a–6f and 7a–
7d with cobaltocene, sodium naphthalide, magnesium and zinc
either in CH2Cl2 or acetonitrile.
Since the electroanalytical data of4a, 4f, 4g and 5a revealed that
the cobalt trithiocarbonates could be easily oxidized, we reacted 4a
and 5a with [Fe(C5H5)2]BF4 and [Fe(C5H5)2]PF6 in CH2Cl2 at room
temperature. After evaporation of the solvent and extraction of
ferrocene from the residue, red brown solids were obtained. They
analyzed as the BF4 and PF6 salts of the radical cations [(C5R5)Co
(PMe3)(S2CS)]+ (8a,b and 9a,b; see Scheme 5). In contrast to 4a
and 5a, the dark brown solids 8a,b and 9a,b are air-sensitive and
readily soluble only in nitromethane. They are almost insoluble
in acetone, CH2Cl2 and THF. The conductivity of 8a,b and 9a,b in
nitromethane corresponds to that of 1:1 electrolytes. Unexpect-
edly, the 1H and 31P NMR spectra of 8a,b and 9a,b displayed rather
sharp signals, despite the presence of one unpaired electron in the
formally cobalt(IV) cation. Even the 1H,31P coupling for the reso-
nance of the PCH3 protons could be determined. We note that para-
magnetic sandwich compounds of cobalt(II) show also relatively
sharp lines in the 1H and 13C spectra, which has been explained
by spin delocalization of the unpaired electron in the metallocene
frontier orbitals [21]. In the case of 8a,b and 9a,b we assume, that
the unpaired electron is mainly localized in the trithiocarbonate li-
gand and much less at the metal atom. The reactions of 8b and 9b
with cobaltocene in the ratio of 1:1 resulted in the quantitative ref-
ormation of the cobalt(III) complexes 4a and 5a, which is consis-
tent with the proposed structure of the cationic species.
and 2.252(3) Å) [8] and [(C5H5)Co(PMe3)(g
2-CS2)] (2.24(0) Å)
[2a]. The Co–S distances in cobalt dithiolene complexes are signif-
icantly shorter than in 11b and lie between 2.12 and 2.14 Å [6,26].
The bond length C–O of 1.211(5) Å corresponds to a carbon–oxy-
gen double bond and is agreement with data of other dithiocarbo-
nato metal compounds [27].
The N-cyanodithiocarbimate complexes 15a and 15b, which
compared with 10a–c and 11a,b contain an exocyclic NCN unit in-
stead of the oxygen atom at the four-membered ring, were pre-
pared from 1c, 3c and K2[S2C@NCN] (Scheme 7). After separation
of by-products by column chromatography, they were isolated as
dark violet, air-stable solids in 67% and 76% yield. The most typical
spectroscopic data of 15a and 15b are the C„N and C@N stretching
modes at, respectively, 2170 and 1440–1445 cmꢀ1 in the IR and the
absorption at 518 nm in the UV spectra, the latter being somewhat
shifted to higher wavelengths compared with 10a and 11a.
The synthesis of the 1,1-dicyanoethylene-2,2-dithiolate cobalt
compounds 16a–e, of which some isomers with maleonitriledithi-
olate as chelating ligand were known [28], and of 17a–d occurred
on a similar route as used for 15a and 15b (Scheme 7). The deeply
coloured solids are air-stable and soluble in chlorinated hydrocar-
bons; the pentamethylcyclopentadienyl derivatives 17a–d are bet-
ter soluble than their cyclopentadienyl counterparts 16a–e.
Similar to some 1,1-dicyanoethylene-2,2-dithiolate palladium
and platinum complexes [27a], the IR spectra of 16a–e and 17a–
d display a strong m m(C@C) mode
(C„N) mode at 2200 cmꢀ1 and a
at 1400–1410 cmꢀ1. The characteristic UV band appears at 512–
535 nm and thus at similar wavelengths as for the analogous tri-
thiocarbonates 4a and 5a–d.
Our attempts to use the cobalt dithiocarbonates 10a–c and
11a,b as precursors to obtain tetrathiofulvalene analogues of type
B equally failed. Similar to the procedure developed by Manning
and co-workers [8], 10a–c and 11a,b were prepared from the di-
iodides 1a,f,g and 3a,b and isolated in good yields (Scheme 6). In
contrast to Manning’s results [8], the deeply coloured, air-stable
solids did not contain solvent molecules and analyzed as calculated
for 10a–c and 11a,b. The IR spectra of 10a–c and 11a,b showed
two strong absorption bands at, respectively, 1580–1590 cmꢀ1
In the course of attempting to obtain 1:1 adducts between 5a as
an electron donor and tetracyanoethylene (TCNE) as an electron
acceptor, we found that both starting materials reacted in CH2Cl2
to give 17a in 81% yield (Scheme 8). The same complex was ob-
tained from 7a and CH2(CN)2 in the presence of NaOMe. A similar
1
Tables with selected bond distances and bond angles, the atomic parameters x, y,
and 1680–1700 cmꢀ1, of which the first is assigned to the
vibration. The second band at higher frequencies has been
m(C@O)
z, the isotropic temperature factors U(eq), and the anisotropic temperature factors
U11, U22, U33, U12, U13, U23 are available on request from the corresponding author.

16
H. Werner, L. Scheller / Polyhedron 34 (2012) 13–23
R
R
R
R
R
K[S2COMe]
Co
1a, f, g; 3a, b
S
L
S
C
O
R
H
H
H
L
10a-c; 11a,b
R
L
10a
10b
10c
PMe3
CNMe
CNPh
11a
11b
Me PMe3
Me PMe2Ph
R
R
R
R
R
P(OR')3
Co
10b, 11a
S
(R'O)3P
S
C
O
12: R = H; R' = Et
13: R = Me; R' = Me
2 Me3SiCl
[(C5R5)Co(PMe3)Cl2]
10a, 11a
14a: R = H; 14b: R = Me
Scheme 6.
procedure was used by Yonemoto and co-workers for the prepara-
tion of dicyanomethylene-1,4,2-dithiazoles from 1,4,2-dithiazoli-
um perchlorates [29]. With regard to the formation of 17a from
5a and TCNE, we assume that the reaction proceeds by a [2+2]
cycloaddition via a four-membered thietane intermediate I. Previ-
ously, intermediates of this type have been observed on treating
thioketones or thioketenes with electron poor olefins [30].
The preparation of the cobalt 1,1-dicyanoethylene-2,2-diselen-
olates 18a and 18b occurred analogously as reported for 16a and
16b (Scheme 9). The chemical properties as well as the spectro-
scopic data of 18a and 18b revealed only minor differences to
those of the 2,2-dithiolates 16a and 16b. We note that whereas
some square-planar silver(I), nickel(II), palladium(II) and plati-
num(II) complexes with [Se2C@C(CN)2]2ꢀ were described [31,32],
related half-sandwich type compounds with this dianion as chelat-
ing ligand, to the best of our knowledge, were unknown.
To compare the reactivity of the cobalt trithiocarbonates 4 and 5
with some rhodium and iridium counterparts, we prepared the
model compounds 20a,b and 22 as shown in Scheme 10. As expected
for complexes of the 4d and 5d elements, they are less deeply col-
oured than the 3d analogues, but air-stable too. The spectroscopic
data are similar to those of 4a and 5d. The same is true for the meth-
ylated species 23a,b and 24, which were obtained from 20a,b and 22
and Meerwein’s reagent [OMe3]BF4. The reactions of 20a,b and
23a,b with P(OEt)3 and zinc did not lead to tetrathiofulvalene ana-
logues of type B; only decomposition was observed.
The oxidation potentials of most of the half-sandwich type com-
plexes reported in this study were determined by cyclovoltammetry.
All compounds showed irreversible oxidation waves in acetonitrile at
room temperature. As summarized in Table 1, the Epa values for the
cyclopentadienyl cobalt trithiocarbonates [(C5H5)Co(L)(S2C@S)]
(4a,f,g) increase in the order L = PMe3 < CNMe < CNPh, which is in
agreement with the decreasing donor and increasing acceptor charac-
ter of L. The same tendency is perceptible for the dithiocarbonates 10a
and 10b. By comparing the analogues 4a and 5a, 10a and 11a, 15a and
15b, 16a and 17a, 18a and 18b, the Epa values for the pentamethylcy-
clopentadienyl compounds are always lower than those of the cyclo-
pentadienyl counterparts. This is in agreement with the increasing
donor strength by substituting hydrogen for methyl at the five-mem-
bered ring. The tertiary phosphine ligand has only a minor influence
on the oxidation potentials, as is illustrated by the Epa values for
16a–d and 17a–d. As expected, the Epa value of the triphenylphosphite
derivative 16e is significantly higher than that of the triphenylphos-
phine analogue 16d. If we accept that the donor ability of the trialkyl-
phosphines PMe3 and PiPr3 is nearly the same, the Epa values of 4a and
22 point to an increase from the 3d to the 5d element. We finally note

H. Werner, L. Scheller / Polyhedron 34 (2012) 13–23
17
R
R
R
R
R
R
R
R
K2[S2C NCN]
K2[Se2C=C(CN)2]
R
R
Co
1c, 3c
Co
1a, 3a
S
Ph2MeP
Se
S
Me3P
C
Se
C
N
CN
CN
C
15a: R = H; 15b: R = Me
NC
18a; R = H; 18b: R = Me
R
R
R
R
Scheme 9.
R
K2[S2C C(CN)2]
1a-1e, 3a-3d
Co
S
L
R
R
R
S
C
R
R
R
R
R
CN
C
R
R
K2CS3
NC
M
M
S
X
R'3P
R'3P
S
C
X
16a-16e, 17a-17d
R
L
R
Me PMe3
17b Me PMe2Ph
L
S
17a
16a
16b
16c
16d
16e
H
H
H
H
H
PMe3
19a, 19b: X = Cl
21: X = I
20a, 20b; 22
PMe2Ph
PMePh2
PPh3
Me PMePh2
Me PPh3
17c
17d
R
BF4
P(OPh)3
R
R
R
R
[OMe3]BF4
Scheme 7.
M
S
C
R'3P
S
SMe
23a, 23b; 24
M
R
H
PR'3
Me
19a, 20a, 23a Rh
PiPr3
Me
Me
Me
Me
Rh
Ir
19b, 20b, 23b
21, 22, 24
Me PPh3
PiPr3
H
TCNE
Co
5a
S
Scheme 10.
Me3P
S
S
C
CN
NC
C
C
cant, for the nickel and platinum complexes [M{Se2C2(CN)2}]2ꢀ and
[M{S2C2(CN)2}]2ꢀ (M = Ni, Pt) [32c].
CN
NC
In summarizing, the present work revealed that, in addition to Man-
ning’s half-sandwich type cyclopentadienyl cobalt complexes with tri-
thiocarbonate as chelating ligand [8], related compounds with
dithiocarbonate, N-cyanodithiocarbimato, 1,1-dicyanoethylene-2,2-
dithiolate and 1,1-dicyanoethylene-2,2-diselenolate were also accessi-
ble. While attempts to convert the complexes with [(C5R5)Co(L)] (R = H,
I
[OMe3]BF4
- {S=C(CN)2}
Me; L = PR3, P(OR)3, CNR) as molecular unit and [S2C@S]2ꢀ, [S2C@O]2ꢀ
,
Me
Me
[S2C@NR]2ꢀ as ligands either directly or via the methylated cationic
species to metalated analogues of tetrathiofulvalenes failed, the
trithiocarbonate derivatives [(C5R5)Co(PMe3)(S2C@S)] could be
oxidized with ferricinium salts to the cationic compounds [(C5R5)Co
(PMe3)(S2CS)]X. Cyclic voltammetry showed that the oxidation
potentials of the title complexes with L = PR3 depend only slightly on
the donor capability of the phosphine ligand. Increasing the donor
strength of either the five-membered ring or the monodentate ligand
L led to a decrease in the oxidation potential which is consistent with
the generally accepted bonding concepts [33].
Me
CH2(CN)2
NaOMe
Me
Me
7a
Co
S
Me3P
S
C
CN
C
NC
17a
Scheme 8.
3. Experimental
that the 1,1-dicyanoethylene-2,2-diselenolates 18a and 18b exhibit
lower oxidation potentials than the 1,1-dicyanoethylene-2,2-dithio-
3.1. General considerations
lates 16a and 17a, which can be rationalized by the lower r-donating
capabilities of the dianion [Se2C2(CN)2]2ꢀ compared with the sulfur
analogue [S2C2(CN)2]2ꢀ. The trend is the same, although less signifi-
All experiments were carried out under an atmosphere of argon
using Schlenk techniques. Solvents were purified and degassed by

18
H. Werner, L. Scheller / Polyhedron 34 (2012) 13–23
Table 1
Oxidation potentials of cyclopentadienyl and pentamethylcyclopentadienyl metal complexes with trithiocarbonate, dithiocarbonate, N-cyanodithiocarbimate, 1,1-dicyanoeth-
ylene-2,2-dithiolate and 1,1-dicyanoethylene-2,2-diselenolate as chelating ligands (in acetonitrile, referenced to the ferrocene/ferricinium redox couple).
Compound
Epa (VFc
)
Compound
Epa [VFc
]
Compound
Epa [VFc
]
Compound
Epa [VFc]
4a
4f
4g
5a
10a
10b
+0.56
+0.74
+0.62
+0.46
+1.01
+1.29
11a
11b
15a
15b
16a
16b
+0.84
+0.89
+1.25
+1.12
+1.21
+1.21
16c
16d
16e
17a
17b
17c
+1.20
+1.25
+1.37
+1.05
+1.07
+1.06
17d
18a
18b
20b
22
+1.13
+1.09
+0.95
+0.90
+0.66
standard procedures. The starting materials 1a [34], 1b,c [35], 1d
[36], 1e,f [37], 1g [38], 2a [36,39], 2b [40], 3b [9], 4b–4e [8], 17a
[41], 17b [42], and 19 [43] were prepared as described in the liter-
ature. NMR spectra were recorded on Bruker WH 90 and AC 200
instruments, IR spectra on a Perkin-Elmer 1420, and UV spectra
on a Hitachi 340 spectrometer. For the X-ray analysis an Enraf Non-
Found: C, 47.43; H, 4.18; Co, 8.14%. The NMR spectroscopic data
were identical with those described by King et al. [10].
3.4. Preparation of [(C5H5)Co(PMe3)(S2C@S)] (4a)
A solution of 1a (136 mg, 0.30 mmol) in 25 ml of CH2Cl2 was trea-
ted with K2CS3 (56 mg, 0.30 mmol) andstirred for 16 h at r.t. The solu-
tion was filtered and the filtrate was brought to dryness in vacuo. The
remaining red-violet microcrystalline solid was washed twice with
3 ml of diethyl ether and dried in vacuo: yield 64 mg (69%), m.p.
89 °C (dec.). Anal. Calc. for C9H14CoPS3: C, 35.06; H, 4.58; S, 31.20;
Co, 19.11. Found: C, 35.34; H, 4.65; S, 30.65; Co, 18.91%. IR (KBr):
ius CAD4 diffractometer with Mo K
a radiation (0.70930 Å), a
graphite monochromator and a zirconium filter (factor 16.55) were
used. Melting points were determined by Differential Thermal
Analysis (DTA). The mass spectra were measured on a Varian
MAT instrument (electron energy 70 eV). Conductivity measure-
ments were carried out in nitromethane with a Schott Kondukto-
meter CG 851. Abbreviations used: s, singlet; d, doublet; t,
triplet; q, quartet; vt, virtual triplet; m, multiplet; br, broadened
signal; coupling constants J and N [N = 3J(P,H) + 5J(P,H)] in Hz.
m
(C@S) 1030 cmꢀ1. UV (CH2Cl2, 10ꢀ6 mol/l): k = 356, 512 nm. 1H
NMR (CDCl3, 90 MHz): d 5.08 (s, 5H, C5H5), 1.56 [d, 2J(PH) = 11.0, 9H,
PMe3]. 31P NMR (CDCl3, 36.2 MHz): d 20.7 (s).
3.2. General procedure for the preparation of [(C5Me5)Co(PR3)I2] (3a–
3c)
3.5. Preparation of [(C5H5)Co(CNMe)(S2C@S)] (4f)
This compound was prepared as described for 4a, with 63 mg
(0.15 mmol) of 1b and 56 mg (0.30 mmol) of K2CS3 as starting
materials; reaction time 3 h. Red brown solid, yield 28 mg (68%),
m.p. 144 °C (dec.). Anal. Calc. for C8H8CoNS3: C, 35.16; H, 2.95; N,
5.13; S, 35.20; Co, 21.56. Found: C, 34.84; H, 2.90; N, 4.90; S,
A solution of 2a (476 mg, 1.00 mmol) in 40 ml of CH2Cl2 was
treated dropwise with a solution of 1.10 mmol of PR3 in 20 ml of
CH2Cl2 and stirred for 6 h at r.t. The solution was concentrated to
10 ml in vacuo, and then layered with 60 ml of diethyl ether. After
the mixture was stored for 12 h at ꢀ20 °C, a microcrystalline solid
precipitated. The mother liquor was decanted, the residue washed
twice with 5 ml of diethyl ether and dried in vacuo. The time of
reaction for 3c was 16 h.
35.22; Co, 21.20%. IR (KBr): m(C„NMe) 2220, m .
(C@S) 1035 cmꢀ1
UV (CH2Cl2, 10ꢀ6 mol/l): k = 340, 492 nm. 1H NMR (CDCl3,
90 MHz): d 5.28 (s, 5H, C5H5), 3.52 (s, 3H, NCH3).
3a: Dark brownish solid; yield 461 mg (88%), m.p. 120 °C (dec.).
Anal. Calc. for C13H24CoI2P: C, 29.79; H, 4.62; Co, 11.25. Found: C,
30.12; H, 4.99; Co, 11.05%. MS (70 eV) m/z 524 (M+), 397 (M+ꢀI),
194 (C5Me5Co+). 1H NMR (CDCl3, 90 MHz): d 1.89 [d, 4J(PH) = 1.5,
15H, C5Me5], 1.83 [d, 2J(PH) = 11.0, 9H, PMe3]. 31P NMR (CDCl3,
36.2 MHz): d 8.8 (s).
3b: Black solid, yield 492 mg (84%), m.p. 75 °C (dec.). Anal. Calc.
for C18H26CoI2P: C, 36.89; H, 4.47; Co, 10.05. Found: C, 37.44; H,
4.69; Co, 9.89%. 1H NMR (CDCl3, 90 MHz): d 7.38–8.32 (br m, 5H,
C6H5), 2.08 [d, 2J(PH) = 10.3, 6H, PCH3], 1.68 [d, 4J(PH) = 1.5, 15H,
C5Me5]. 31P NMR (CDCl3, 36.2 MHz): d 12.2 (s).
3.6. Preparation of [(C5H5)Co(CNPh)(S2C@S)] (4g)
This compound was prepared as described for 4a, with 72 mg
(0.15 mmol) of 1c and 56 mg (0.30 mmol) of K2CS3 as starting
materials; reaction time 3 h. Red brown solid, yield 31 mg (62%),
m.p. 78 °C (dec.). Anal. Calc. for C13H10CoNS3: C, 46.56; H, 3.01;
N, 4.18; S, 19.12; Co, 17.57. Found: C, 46.46; H, 2.87; N, 3.99; S,
19.21; Co, 16.94%. IR (KBr): m(C„NMe) 2175, m .
(C@S) 1030 cmꢀ1
UV (CH2Cl2, 10ꢀ6 mol/l): k = 339, 494 nm. 1H NMR (CDCl3,
90 MHz): d 7.38 (br m, 5H, C6H5), 5.40 (s, 5H, C5H5).
3c: Dark greenish solid, yield 551 mg (85%), m.p. 79 °C (dec.).
Anal. Calc. for C23H28CoI2P: C, 42.62; H, 4.35; Co, 9.09. Found: C,
43.04; H, 4.49; Co, 8.72%. 1H NMR (CDCl3, 90 MHz): d 7.33–8.08
(br m, 10H, C6H5), 2.34 [d, 2J(PH) = 9.8, 3H, PCH3], 1.68 [d,
4J(PH) = 1.7, 15H, C5Me5]. 31P NMR (CDCl3, 36.2 MHz): d 25.5 (s).
3.7. Preparation of [(C5H5)Co{P(OEt)3}(S2C@S)] (4h)
(a) A solution of 4b (109 mg, 0.22 mmol) in 25 ml of benzene
was treated with P(OEt)3 (382 ll, 2.20 mmol) and stirred for 2 d
at 40 °C. After the solution was cooled to r.t., it was filtered and
the filtrate was brought to dryness in vacuo. The remaining red
microcrystalline solid was washed three times with 3 ml of a mix-
ture of hexane/diethyl ether (3:1) and dried in vacuo: yield 47 mg
(54%). (b) A suspension of 4a (65 mg, 0.21 mmol) in 10 ml of ben-
zene was treated with P(OEt)3 (1.00 ml, 6.30 mmol) and stirred for
3 d at 70 °C. After the solution was cooled to r.t., it was worked up
as described for (a): yield 38 mg (46%). (c) A solution of 4d (52 mg,
0.19 mmol) in 20 ml of benzene was treated with P(OEt)3 (0.33 ml,
1.90 mmol) and stirred for 18 h at r.t. It was then worked up as de-
scribed for (a): yield 61 mg (81%), m.p. 86 °C (dec.). Anal. Calc. for
3.3. Preparation of [(C5Me5)Co(PPh3)I2] (3d)
A solution of 2b (515 mg, 1.15 mmol) in 40 ml of CH2Cl2 was
treated under stirring with PPh3 (603 mg, 2.30 mmol), which led
to a quick change of colour from black to green. The solution was
continuously stirred for 5 min at r.t., then filtered and the filtrate
was brought to dryness in vacuo. The remaining green microcrys-
talline solid was washed three times with 3 ml of a mixture of hex-
ane/diethyl ether (3:1) and dried in vacuo: yield 1.57 g (96%), m.p.
112 °C (dec.). Anal. Calc. for C28H30CoI2P: C, 47.35; H, 4.26; Co, 8.30.
C12H20CoO3PS3: C, 36.18; H, 5.06; S, 24.15; Co, 14.79. Found: C,

H. Werner, L. Scheller / Polyhedron 34 (2012) 13–23
19
36.29; H, 5.03; S, 23.82; Co, 14.51%. IR (KBr):
m
(C@S) 1030 cmꢀ1. 1H
5.15 (s, 5H, C5H5), 4.05 [dq,
H, 4.18; S, 23.45; Co, 14.37. Found: C, 29.34; H, 4.53; S, 23.19;
NMR (CDCl3, 90 MHz):
d
Co, 13.91%. IR (KBr): m
(C@S) 990 cmꢀ1. UV (CH2Cl2, 10ꢀ6 mol/l):
3J(PH) = 3J(HH) = 7.1, 6H, CH2], 1.29 [t, 3J(HH) = 7.1, 9H, CH3].
k = 568 nm. 1H NMR (CD3NO2, 90 MHz): d 5.57 [d, 3J(PH) = 0.7,
5H, C5H5], 2.76 (s, 3H, SCH3), 1.71 [d, 2J(PH) = 11.7, 9H, PMe3]. 13C
NMR (CD3NO2, 50.3 MHz): d 88.7 (s, C5H5), 17.1 (s, SCH3), 16.6 [d,
1J(PC) = 34.7, PMe3], signal of S2C carbon atom not exactly located.
31P NMR [(CD3)2CO, 36.2 MHz]: d 22.8 (s).
3.8. Preparation of [(C5Me5)Co(PMe3)(S2C@S)] (5a)
A solution of 3a (131 mg, 0.25 mmol) in 25 ml of CH2Cl2 was
treated with K2CS3 (93 mg, 0.50 mmol) and stirred for 5 h at r.t.
The solution was filtered and the filtrate was brought to dryness
in vacuo. The remaining dark red microcrystalline solid was
washed three times with 3 ml of diethyl ether and dried in vacuo:
yield 62 mg (66%), m.p. 133 °C (dec.). Anal. Calc. for C14H24CoPS3: C,
44.43; H, 6.39; S, 25.42; Co, 15.57. Found: C, 43.97; H, 6.51; S,
25.08; Co, 14.97%. MS (70 eV) m/z 378 (M+), 194 (C5Me5Co+). IR
6b: Dark brown solid, yield 139 mg (84%), m.p. 102 °C (dec.),
K
= 74 cm2 ꢀ1 molꢀ1. Anal. Calc. for C15H19BCoF4PS3: C, 38.15;
X
H, 4.06; S, 20.37; Co, 12.48. Found: C, 38.30; H, 3.93; S, 20.61;
Co, 12.13%. IR (KBr): m
(C@S) 990 cmꢀ1. UV (CH2Cl2, 10ꢀ6 mol/l):
k = 574 nm. 1H NMR (CD3NO2, 90 MHz): d 7.37–7.68 (br m, 5H,
C6H5), 5.49 [d, 3J(PH) = 0.7, 5H, C5H5], 2.60 (s, 3H, SCH3),
2.08 [d, 2J(PH) = 10.5, 6H, PCH3]. 31P NMR [(CD3)2CO, 36.2 MHz]:
d 27.0 (s).
(KBr): m
(C@S) 1030, 1020 cmꢀ1. UV (CH2Cl2, 10ꢀ6 mol/l): k = 361,
502 nm. 1H NMR (CDCl3, 90 MHz): d 1.57 [d, 4J(PH) = 1.7, 15H,
C5Me5], 1.42 [d, 2J(PH) = 10.0, 9H, PMe3]. 31P NMR (CDCl3,
36.2 MHz): d 13.2 (s).
6c: Dark brown solid, yield 166 mg (89%), m.p. 150 °C (dec.),
K
= 73 cm2 ꢀ1 molꢀ1. Anal. Calc. for C20H21BCoF4PS3: C, 44.96;
X
H, 3.96; S, 18.00; Co, 11.03. Found: C, 44.81; H, 4.14; S, 18.31;
Co, 10.66%. IR (KBr): m
(C@S) 990 cmꢀ1. UV (CH2Cl2, 10ꢀ6 mol/l):
3.9. Preparation of [(C5Me5)Co(PMe2Ph)(S2C@S)] (5b)
k = 572 nm. 1H NMR (CD3NO2, 90 MHz): d 7.52–7.71 (br m, 10H,
C6H5), 5.59 [d, 3J(PH) = 0.5, 5H, C5H5], 2.60 [d, 2J(PH) = 10.5, 3H,
PCH3], 2.40 (s, 3H, SCH3). 31P NMR [(CD3)2CO, 36.2 MHz]: d 36.4 (s).
6d: Dark brown solid, yield 182 mg (87%), m.p. 54 °C (dec.),
This compound was prepared as described for 5a, with 147 mg
(0.25 mmol) of 3b and 93 mg (0.50 mmol) of K2CS3 as starting
materials; reaction time 6 h. Red violet solid, yield 77 mg (70%),
m.p. 86 °C (dec.). Anal. Calc. for C14H24CoPS3: C, 51.81; H, 5.95; S,
21.84; Co, 13.38. Found: C, 51.34; H, 6.09; S, 22.09; Co, 12.89%.
K
= 81 cm2 ꢀ1 molꢀ1. Anal. Calc. for C25H23BCoF4PS3: C, 48.33;
X
H, 3.89; S, 16.13; Co, 9.88. Found: C, 48.68; H, 3.66; S, 16.37; Co,
9.57%. IR (KBr):
m .
(C@S) 990 cmꢀ1 UV (CH2Cl2, 10ꢀ6 mol/l):
IR (KBr):
m
(C@S) 1030, 1020 cmꢀ1
.
UV (CH2Cl2, 10ꢀ6 mol/l):
k = 574 nm. 1H NMR (CD3NO2, 90 MHz): d 7.48–7.93 (br m, 15H,
C6H5), 5.49 (s, 5H, C5H5], 2.37 (s, 3H, SCH3). 31P NMR [(CD3)2CO,
36.2 MHz]: d 46.4 (s).
k = 362, 512 nm. 1H NMR (CDCl3, 90 MHz): d 7.40–7.55 (br m, 5H,
C6H5), 1.42 [d, 2J(PH) = 9.8, 6H, CH3], 1.30 [d, 4J(PH) = 1.7, 15H,
C5Me5]. 31P NMR (CDCl3, 36.2 MHz): d 23.2 (s).
6e: Red brown solid, yield 113 mg (86%), m.p. 94 °C (dec.),
K
= 80 cm2 ꢀ1 molꢀ1. Anal. Calc. for C9H11BCoF4NS3: C, 28.82; H,
X
3.10. Preparation of [(C5Me5)Co(PMePh2)(S2C@S)] (5c)
2.96; N, 3.73; S, 25.64; Co, 15.71. Found: C, 29.04; H, 2.78; N,
3.97; S, 25.44; Co, 15.41%. IR (KBr):
m(C„NMe) 2240, m(C@S)
This compound was prepared as described for 5a, with 162 mg
(0.25 mmol) of 3c and 93 mg (0.50 mmol) of K2CS3 as starting
materials; reaction time 8 h. Dark violet solid, yield 92 mg (73%),
m.p. 73 °C (dec.). Anal. Calc. for C24H28CoPS3: C, 57.36; H, 5.62; S,
19.14; Co, 11.73. Found: C, 57.11; H, 5.70; S, 18.75; Co, 11.37%.
990 cmꢀ1. UV (CH2Cl2, 10ꢀ6 mol/l): k = 576 nm. 1H NMR (CD3NO2,
90 MHz): d 5.80 (s, 5H, C5H5), 2.80 (s, 3H, SCH3), 3.70 (br s, 3H,
NCH3).
6f: Dark brown solid, yield 122 mg (80%), m.p. 144 °C (dec.),
K
= 78 cm2 ꢀ1 molꢀ1. Anal. Calc. for C14H13BCoF4NS3: S, 22.00;
X
IR (KBr):
m
(C@S) 1035, 1020 cmꢀ1
.
UV (CH2Cl2, 10ꢀ6 mol/l):
Co, 13.48. Found: S, 21.78; Co, 13.51%. IR (KBr):
m(C„NPh) 2180,
k = 361, 516 nm. 1H NMR (CDCl3, 90 MHz): d 7.45–7.85 (br m,
10H, C6H5), 1.60 [d, 2J(PH) = 8.3, 3H, CH3], 1.26 [d, 4J(PH) = 1.7,
15H, C5Me5]. 31P NMR (CDCl3, 36.2 MHz): d 41.2 (s).
m
(C@S) 990 cmꢀ1 1H NMR (CD3NO2, 90 MHz): d 7.40–7.68 (br m,
.
15H, C6H5), 5.91 (s, 5H, C5H5), 2.81 (s, 3H, SCH3).
7a: Red brown solid, yield 145 mg (86%), m.p. 97 °C (dec.),
K
= 73 cm2 ꢀ1 molꢀ1. Anal. Calc. for C15H27BCoF4PS3: C, 37.51;
X
3.11. Preparation of [(C5Me5)Co(PPh3)(S2C@S)] (5d)
H, 5.67; S, 20.03; Co, 12.27. Found: C, 38.06; H, 5.80; S, 20.59;
Co, 12.00%. IR (KBr):
m
(C@S) 980 cmꢀ1. UV (CH2Cl2, 10ꢀ6 mol/l):
This compound was prepared as described for 5a, with 178 mg
(0.25 mmol) of 3d and 93 mg (0.50 mmol) of K2CS3 as starting
materials; reaction time 10 h. Red violet solid, yield 45 mg (32%),
m.p. 156 °C (dec.). Anal. Calc. for C29H30CoPS3: C, 61.69; H, 5.36;
S, 17.04; Co, 10.44. Found: C, 62.13; H, 5.28; S, 16.68; Co, 10.35%.
k = 580 nm. 1H NMR (CD3NO2, 90 MHz): d 2.77 (s, 3H, SCH3), 1.66
[d, 4J(PH) = 1.7, 15H, C5Me5], 1.56 [d, 2J(PH) = 10.5, 9H, PMe3]. 13C
NMR (CD3NO2, 50.3 MHz): d 97.1 (s, C5Me5), 17.1 (s, SCH3), 13.9
[d, 1J(PC) = 31.6, PMe3], 9.3 (s, CCH3), signal of S2C carbon atom
not exactly located. 31P NMR [(CD3)2CO, 36.2 MHz]: d 11.1 (s).
7b: Dark brown solid, yield 156 mg (82%), m.p. 99 °C (dec.),
IR (KBr):
m .
(C@S) 1030, 1020 cmꢀ1 UV (CH2Cl2, 10ꢀ6 mol/l):
k = 360, 524 nm. 1H NMR (CDCl3, 90 MHz): d 7.25–7.65 (br m,
15H, C6H5), 1.30 [d, 4J(PH) = 1.7, 15H, C5Me5]. 31P NMR (CDCl3,
36.2 MHz): d 49.6 (s).
K X
= 64 cm2 ꢀ1 molꢀ1. Anal. Calc. for C20H29BCoF4PS3: C, 44.29;
H, 5.39; S, 17.74; Co, 10.87. Found: C, 44.63; H, 5.46; S, 18.01;
Co, 10.84%. IR (KBr): m
(C@S) 980 cmꢀ1. UV (CH2Cl2, 10ꢀ6 mol/l):
k = 580 nm. 1H NMR (CD3NO2, 90 MHz): d 7.48–7.65 (br m, 5H,
C6H5), 2.75 (s, 3H, SCH3), 1.77 [d, 2J(PH) = 10.0, 6H, PMe2], 1.45
[d, 4J(PH) = 1.7, 15H, C5Me5]. 31P NMR [(CD3)2CO, 36.2 MHz]: d
20.2 (s).
3.12. General procedure for the preparation of
[(C5H5)Co(L)(S2CSMe)BF4 (6a–6f) and [(C5Me5)Co(PR3)(S2CSMe)BF4
(7a–7d)
7c: Dark brown solid, yield 195 mg (92%), m.p. 138 °C (dec.),
A solution of 0.35 mmol of4a–4d, 4f, 4g, 5a–5d in 25 ml of CH2Cl2
was treated under stirring with [Me3O]BF4 (52 mg, 0.35 mmol) and
continuously stirred for 3 h at r.t. The solution was filtered and the
filtrate was brought to dryness in vacuo. The residue was washed
three times with 5 ml of diethyl ether and dried in vacuo.
K X
= 65 cm2 ꢀ1 molꢀ1. Anal. Calc. for C25H31BCoF4PS3: C, 49.68;
H, 5.17; S, 15.91; Co, 9.75. Found: C, 50.29; H, 5.35; S, 16.16; Co,
9.76%. IR (KBr):
m .
(C@S) 985 cmꢀ1 UV (CH2Cl2, 10ꢀ6 mol/l):
k = 580 nm. 1H NMR (CD3NO2, 90 MHz): d 7.42–7.63 (br m,
10H, C6H5), 2.47 [d, 2J(PH) = 9.5, 3H, PCH3], 2.39 (s, 3H, SCH3),
1.50 [d, 4J(PH) = 1.7, 15H, C5Me5]. 31P NMR [(CD3)2CO, 36.2 MHz]:
d 31.1 (s).
6a: Red brown solid, yield 126 mg (88%), m.p. 123 °C (dec.),
K
= 71 cm2 ꢀ1 molꢀ1. Anal. Calc. for C10H17BCoF4PS3: C, 29.28;
X

20
H. Werner, L. Scheller / Polyhedron 34 (2012) 13–23
7d: Dark brown solid, yield 196 mg (84%), m.p. 113 °C (dec.),
= 63 cm2 ꢀ1 molꢀ1. Anal. Calc. for C30H33BCoF4PS3: C, 54.06;
k = 406, 506 nm. 1H NMR (CDCl3, 90 MHz): d 5.28 (s, 5H, C5H5),
3.51 (s, 3H, NCH3).
K
X
H, 4.99; S, 14.43; Co, 8.84. Found: C, 54.07; H, 5.11; S, 14.39; Co,
10c: Red violet solid, yield 65 mg (68%), m.p. 67 °C (dec.). Anal.
Calc. for C13H10CoNOS2: C, 48.90; H, 3.16; N, 4.39; S, 20.08; Co,
18.46. Found: C, 48.87; H, 3.17; N, 4.39; S, 19.91; Co, 18.36%. IR
9.20%. IR (KBr):
m .
(C@S) 985 cmꢀ1 UV (CH2Cl2, 10ꢀ6 mol/l):
k = 590 nm. 1H NMR (CD3NO2, 90 MHz): d 7.37–7.82 (br m, 15H,
C6H5), 2.37 (s, 3H, SCH3), 1.33 [d, 4J(PH) = 1.7, 15H, C5Me5]. 31P
NMR [(CD3)2CO, 36.2 MHz]: d 47.9 (s).
(KBr):
m(C„N) 2170, m . UV (CH2Cl2,
(C@O) 1580, 1695 cmꢀ1
10ꢀ6 mol/l): k = 408, 506 nm. 1H NMR (CDCl3, 90 MHz): d 6.38
(m, 5H, C6H5), 5.39 (s, 5H, C5H5).
11a: Red violet solid, yield 85 mg (78%), m.p. 158 °C (dec.). Anal.
Calc. for C14H24CoOPS2: C, 46.40; H, 6.68; S, 17.70; Co, 16.26.
Found: C, 46.76; H, 6.83; S, 17.93; Co, 15.88%. MS (70 eV) m/z
3.13. General procedure for the preparation of [(C5H5) Co(PMe3)-
(S2CS)]X (8a, 8b) and [(C5Me5)Co(PMe3)(S2CS)]X (9a, 9b)
362 (M+), 286 (M+ꢀPMe3), 194 (C5Me5Co+). IR (KBr):
m(C@O)
A
suspension of 4a (80 mg, 0.26 mmol) or 5a (98 mg,
1585, 1700 cmꢀ1. UV (CH2Cl2, 10ꢀ6 mol/l): k = 382, 504 nm. 1H
NMR (CDCl3, 90 MHz): d 1.57 [d, 4J(PH) = 1.5, 15H, C5Me5], 1.41
[d, 2J(PH) = 9.8, 9H, PMe3]. 31P NMR (CDCl3, 36.2 MHz): d 21.4 (s).
11b: Dark violet solid, yield 98 mg (77%), m.p. 86 °C (dec.). Anal.
Calc. for C19H26CoOPS2: C, 53.77; H, 6.17; S, 15.11; Co, 13.88.
0.26 mmol) and [Fe(C5H5)2]BF4 (71 mg, 0.26 mmol) in 15 ml of
CH2Cl2 was stirred for 1 h at r.t. The solvent was evaporated in va-
cuo and the dark brown solid was extracted twice with 10 ml of
benzene. The residue wasꢀwashed three times with 5 ml of diethyl
ether and dried. The PF6 salts were prepared analogously with
[Fe(C5H5)2]PF6 (86 mg, 0.26 mmol) as oxidans.
Found: C, 53.75; H, 6.40; S, 15.15; Co, 13.38%. IR (KBr): m(C@O)
1590, 1685 cmꢀ1. UV (CH2Cl2, 10ꢀ6 mol/l): k = 376, 506 nm. 1H
NMR (CDCl3, 90 MHz): d 7.38–7.89 (br m, 5H, C6H5), 1.58 [d,
2J(PH) = 9.8, 6H, PMe2], 1.30 [d, 4J(PH) = 1.7, 15H, C5Me5]. 31P
NMR (CDCl3, 36.2 MHz): d 21.4 (s).
8a: Red brown solid, yield 88 mg (86%), m.p. 151 °C (dec.),
K
= 83 cm2 ꢀ1 molꢀ1. Anal. Calc. for C9H14BCoF4PS3: C, 27.36; H,
X
3.57; S, 24.35; Co, 14.91. Found: C, 26.81; H, 3.58; S, 24.07; Co,
14.51%. IR (KBr):
m
(BF4) 1050 cmꢀ1. UV (CH2Cl2, 10ꢀ6 mol/l):
k = 590 nm. 1H NMR (CD3NO2, 90 MHz): d 5.64 (s, 5H, C5H5), 1.71
[d, 2J(PH) = 11.7, 9H, PMe3]. 31P NMR [(CD3)2CO, 36.2 MHz]: d
19.0 (s).
3.15. Preparation of [(C5H5)Co{P(OEt)3}(S2C@O)] (12)
A solution of 10b (48 mg, 0.19 mmol) in 20 ml of benzene was
treated with P(OEt)3 (330 ll, 1.90 mmol) and stirred for 3 h at r.t.
8b: Red brown solid, yield 95 mg (81%), m.p. 126 °C (dec.),
K
= 69 cm2 ꢀ1 molꢀ1. Anal. Calc. for C9H14CoF6P2S3: C, 23.85; H,
X
The solution was filtered and the filtrate was brought to dryness
in vacuo. The remaining red microcrystalline solid was washed
three times with 3 ml of a mixture of hexane/diethyl ether (3:1)
and dried in vacuo: yield 58 mg (81%), m.p. 103 °C (dec.). Anal. Calc.
for C12H20CoO4PS2: C, 37.70; H, 5.27; S, 16.77; Co, 15.41. Found: C,
3.11; S, 21.22; Co, 13.00. Found: C, 24.24; H, 3.18; S, 20.96; Co,
12.66%. IR (KBr):
m(PF6) 835, m . UV (CH2Cl2,
(CS) 1010 cmꢀ1
10ꢀ6 mol/l): k = 590 nm. 1H NMR (CD3NO2, 90 MHz): d 5.65 (s,
5H, C5H5), 1.73 [d, 2J(PH) = 11.8, 9H, PMe3]. 31P NMR [(CD3)2CO,
36.2 MHz]: d 19.2 (s, PMe3), ꢀ146.4 (sept, PF6).
38.04; H, 5.09; S, 16.79; Co, 14.94%. IR (KBr): m
(C@O) 1585 cmꢀ1. 1H
9a: Red brown solid, yield 108 mg (89%), m.p. 56 °C (dec.),
NMR (CDCl3, 90 MHz):
d
5.16 (s, 5H, C5H5), 4.10 [dq,
K
= 74 cm2 ꢀ1 molꢀ1. Anal. Calc. for C14H24BCoF4PS3: C, 36.15;
X
3J(PH) = 3J(HH) = 7.0, 6H, CH2], 1.31 [t, 3J(HH) = 7.0, 9H, CH3]. 31P
NMR (CDCl3, 36.2 MHz): d 135.4 (br s).
H, 4.20; S, 20.68; Co, 12.69. Found: C, 36.26; H, 4.15; S, 20.41;
Co, 12.52%. IR (KBr): m
(BF4) 1055 cmꢀ1. UV (CH2Cl2, 10ꢀ6 mol/l):
k = 590 nm. 1H NMR (CD3NO2, 90 MHz): d 1.68 (s, 15H, C5Me5),
1.58 [d, 2J(PH) = 10.5, 9H, PMe3]. 31P NMR [(CD3)2CO, 36.2 MHz]:
d 8.0 (s).
3.16. Preparation of [(C5Me5)Co{P(OMe)3}(S2C@O)] (13)
A solution of 11a (87 mg, 0.24 mmol) in 20 ml of benzene was
treated with P(OMe)3 (0.90 ml, 7.20 mmol) and stirred for 3 h un-
der reflux. After the solution was cooled to r.t., the solvent was
evaporated in vacuo. The residue was dissolved in 3 ml of CH2Cl2
and the solution was chromatographed on Al2O3 (neutral, activity
grade V, height of column 3 cm). With CH2Cl2 a dark red fraction
was eluted, from which the solvent was removed. The red micro-
crystalline solid was washed three times with 3 ml of a mixture
of hexane/CH2Cl2 (3:1) and dried in vacuo: yield 60 mg (61%),
m.p. 121 °C (dec.). Anal. Calc. for C14H24CoO4PS2: C, 40.98; H,
5.89; S, 15.63; Co, 14.36. Found: C, 40.49; H, 5.85; S, 15.11; Co,
9b: Red brown solid, yield 120 mg (88%), m.p. 108 °C (dec.),
K
= 91 cm2 ꢀ1 molꢀ1. Anal. Calc. for C14H24CoF6P2S3: C, 32.13; H,
X
4.62; S, 18.38; Co, 11.26. Found: C, 32.23; H, 4.65; S, 18.51; Co,
10.88%. IR (KBr):
m(PF6) 835, m . UV (CH2Cl2,
(CS) 1020 cmꢀ1
10ꢀ6 mol/l): k = 590 nm. 1H NMR (CD3NO2, 90 MHz): d 1.68 (s,
15H, C5Me5), 1.58 [d, 2J(PH) = 10.6, 9H, PMe3]. 31P NMR [(CD3)2CO,
36.2 MHz]: d 8.1 (s, PMe3), ꢀ154.9 (sept, PF6).
3.14. General procedure for the preparation of [(C5H5)Co(L)(S2C@O)]
(10a–10c) and [(C5Me5)Co(PR3)(S2C@O)] (11a, 11b)
14.44%. IR (KBr):
m .
(C@O) 1590, 1680 cmꢀ1 1H NMR (CDCl3,
A suspension of 0.30 mmol of 1a–1c or 3a, 3b and K[S2COMe]
(48 mg, 0.33 mmol) in 25 ml of CH2Cl2 was intensively stirred for
1 h at r.t. The solution was filtered and the filtrate was brought
to dryness in vacuo. The residue was washed three times with
3 ml of diethyl ether and dried in vacuo.
90 MHz): d 3.67 [d, 3J(PH) = 10.2, 9H, POH3], 1.58 [d, 4J(PH) = 1.5,
15H, C5Me5]. 31P NMR (CDCl3, 36.2 MHz): d 146.7 (br s).
3.17. Preparation of [(C5Me5)Co(PMe3)Cl2] (14b)
10a: Dark red solid, yield 63 mg (72%), m.p. 65 °C (dec.). Anal.
Calc. for C9H14CoOPS2: C, 36.99; H, 4.83; S, 21.94; Co, 20.16. Found:
A solution of 11a (91 mg, 0.25 mmol) in 15 ml of CH2Cl2 was
treated with Me3SiCl (0.63 ll, 0.50 mmol) and stirred for 4 h at
C, 36.80; H, 4.63; S, 22.21; Co, 19.78%. IR (KBr):
m
(C@O) 1590,
r.t. The solution was filtered, and the filtrate was brought to dry-
ness in vacuo. The residue was worked up as described for 13.
Red violet solid, yield 47 mg (55%), m.p. 98 °C (dec.). Anal. Calc.
for C13H24Cl2CoP: C, 45.77; H, 7.09; Co, 17.27. Found: C, 45.66; H,
6.86; Co, 17.00%. MS (70 eV) m/z 340 (M+), 305 (M+ꢀCl), 200
(M+ꢀ2Cl). UV (CH2Cl2, 10ꢀ6 mol/l): k = 546 nm. 1H NMR (CDCl3,
90 MHz): d 1.58 [d, 2J(PH) = 11.0, 9H, PMe3] 1.39 [d, 4J(PH) = 1.7,
15H, C5Me5]. 31P NMR (CDCl3, 36.2 MHz): d 14.3 (s).
1690 cmꢀ1. UV (CH2Cl2, 10ꢀ6 mol/l): k = 396, 494 nm. 1H NMR
(CDCl3, 90 MHz): d 5.08 s, 5H, C5H5), 1.54 [d, 2J(PH) = 11.0, 9H,
PMe3]. 31P NMR (CDCl3, 36.2 MHz): d 21.4 (s).
10b: Red violet solid, yield 53 mg (69%), m.p. 64 °C (dec.). Anal.
Calc. for C8H8CoNOS2: C, 37.36; H, 3.13; N, 5.45; S, 24.93; Co, 22.91.
Found: C, 37.08; H, 3.27; N, 5.69; S, 24.61; Co, 22.99%. IR (KBr):
m
(C„N) 2230, m
(C@O) 1590, 1700 cmꢀ1. UV (CH2Cl2, 10ꢀ6 mol/l):

H. Werner, L. Scheller / Polyhedron 34 (2012) 13–23
21
3.18. Preparation of [(C5H5)Co(PMePh2)(S2C@NCN)] (15a)
k = 530 nm. 1H NMR (CDCl3, 90 MHz): d 7.36–7.76 (br m, 15H,
C6H5), 5.01 (s, 5H, C5H5). 31P NMR [CDCl3, 36.2 MHz]: d 46.4 (s).
16e: Red violet solid; yield 83 mg (76%), m.p. 182 °C (dec.). Anal.
Calc. for C27H20CoN2O3PS2: C, 56.45; H, 3.51; N, 4.88; S, 11.16; Co,
10.26. Found: C, 56.51; H, 3.51; N, 4.86; S, 11.03; Co, 10.10%. IR
A solution of 1c (127 mg, 0.22 mmol) in 35 ml of THF was trea-
ted with K2[S2C@NCN] (86 mg, 0.44 mmol) and stirred for 3 h at
70 °C. After the solution was cooled to r.t., it was filtered and the
filtrate was brought to dryness in vacuo. The residue was dissolved
in 5 ml of CH2Cl2 and the solution was chromatographed on Al2O3
(KBr): m(C„N) 2200, m
(C@N) 1410 cmꢀ1. UV (CH2Cl2, 10ꢀ6 mol/l):
k = 518 nm. 1H NMR (CD2Cl2, 90 MHz): d 7.08–7.50 (br m, 15H,
C6H5), 4.85 [d, 3J(PH) = 1.7, 5H, C5H5]. 31P NMR [CDCl3,
36.2 MHz]: d 132.5 (s).
17a: Red violet solid; yield 57 mg (73%), m.p. 115 °C (dec.). Anal.
Calc. for C17H24CoN2PS2: C, 49.75; H, 5.89; N, 6.83; S, 15.63; Co,
14.36. Found: C, 50.39; H, 6.07; N, 6.98; S, 15.58; Co, 14.21%. MS
(neutral, activity grade V, height of column 5 cm). With CH2Cl2
a
violet fraction was eluted, from which the solvent was evaporated.
The dark violet microcrystalline solid was washed three times with
3 ml of a mixture of hexane/CH2Cl2 (3:1) and dried in vacuo: yield
65 mg (67%), m.p. 208 °C (dec.). Anal. Calc. for C20H18CoN2PS2: C,
54.54; H, 4.12; N, 6.36; S, 14.56; Co, 13.38. Found: C, 54.30; H,
(70 eV) m/z 410 (M+), 194 (C5Me5Co+). IR (KBr):
m(C„N) 2200,
4.21; N, 6.08; S, 14.30; Co, 13.06%. IR (KBr):
m
m
(C„N) 2170,
m
(C@N) 1400 cmꢀ1. UV (CH2Cl2, 10ꢀ6 mol/l): k = 512 nm. 1H NMR
(C@N) 1445 cmꢀ1. UV (CH2Cl2, 10ꢀ6 mol/l): k = 518 nm. 1H NMR
(CDCl3, 90 MHz): d 1.54 [d, 4J(PH) = 1.7, 15H, C5Me5], 1.46 [d,
2J(PH) = 10.0, 9H, PCH3]. 31P NMR [CDCl3, 36.2 MHz]: d 12.4 (s).
17b: Violet solid; yield 66 mg (74%), m.p. 124 °C (dec.). Anal.
Calc. for C22H26CoN2PS2: C, 55.92; H, 5.55; N, 5.93; S, 13.57; Co,
12.47. Found: C, 56.09; H, 5.55; N, 6.08; S, 13.40; Co, 12.75%. IR
(CDCl3, 90 MHz): d 7.31–7.89 (br m, 10H, C6H5), 5.01 (s, 5H,
C5H5), 1.77 [d, 2J(PH) = 10.6, 3H, PCH3]. 31P NMR [CDCl3,
36.2 MHz]: d 38.1 (s).
(KBr): m(C„N) 2200, m
(C@N) 1405 cmꢀ1. UV (CH2Cl2, 10ꢀ6 mol/l):
3.19. Preparation of [(C5Me5)Co(PMePh2)(S2C@NCN)] (15b)
k = 512 nm. 1H NMR (CDCl3, 90 MHz): d 7.40–7.70 (br m, 5H,
C6H5), 1.62 [d, 2J(PH) = 10.0, 6H, PCH3], 1.28 [d, 4J(PH) = 1.7, 15H,
C5Me5]. 31P NMR [CDCl3, 36.2 MHz]: d 21.1 (s).
This compound was prepared as described for 15a, with 143 mg
(0.22 mmol) of 3c and 86 mg (0.44 mmol) of K2[S2C@NCN] as start-
ing materials. Dark violet solid, yield 85 mg (76%), m.p. 148 °C
(dec.). Anal. Calc. for C25H28CoN2PS2: C, 58.81; H, 5.53; N, 5.49; S,
12.56; Co, 11.54. Found: C, 58.64; H, 5.44; N, 5.03; S, 12.63; Co,
17c: Violet solid; yield 81 mg (80%), m.p. 173 °C (dec.). Anal.
Calc. for C27H28CoN2PS2: C, 60.67; H, 5.28; N, 5.24; S, 12.00; Co,
11.02. Found: C, 60.42; H, 5.46; N, 5.18; S, 11.97; Co, 10.79%. IR
(KBr): m(C„N) 2200, m
(C@N) 1410 cmꢀ1. UV (CH2Cl2, 10ꢀ6 mol/l):
11.32%. IR (KBr): m(C„N) 2170, m
(C@N) 1440 cmꢀ1. UV (CH2Cl2,
k = 530 nm. 1H NMR (CDCl3, 90 MHz): d 7.32–7.70 (br m, 10H,
C6H5), 1.91 [d, 2J(PH) = 9.4, 3H, PCH3], 1.32 [d, 4J(PH) = 1.7, 15H,
C5Me5]. 31P NMR [CDCl3, 36.2 MHz]: d 32.0 (s).
10ꢀ6 mol/l): k = 518 nm. 1H NMR (CDCl3, 90 MHz): d 7.28–7.76
(br m, 10H, C6H5), 1.76 [d, 2J(PH) = 9.8, 3H, CH3], 1.30 [d,
4J(PH) = 1.7, 15H, C5Me5]. 31P NMR (CDCl3, 36.2 MHz): d 36.7 (s).
17d: Red solid; yield 69 mg (61%), m.p. 198 °C (dec.). Anal. Calc.
for C32H30CoN2PS2: S, 10.75; Co, 9.88. Found: S, 10.88; Co, 9.78%. IR
3.20. General procedure for the preparation of
[(C5H5)Co(PR3){S2C@C(CN)2}] (16a–16e) and
[(C5Me5)Co(PR3){S2C@C(CN)2}] (17a–17d)
(KBr): m(C„N) 2200, m
(C@N) 1410 cmꢀ1. UV (CH2Cl2, 10ꢀ6 mol/l):
k = 535 nm. 1H NMR (CDCl3, 90 MHz): d 7.27–7.66 (br m, 15H,
C6H5), 1.21 [d, 4J(PH) = 1.7, 15H, C5Me5]. 31P NMR [CDCl3,
36.2 MHz]: d 46.3 (s).
A suspension of 0.19 mmol of [(C5H5)Co(PR3)I2] (1a–1e) or
[(C5Me5)Co(PR3)I2] (3a–3d) in 25 ml of a mixture of CH2Cl2/THF
(3:1) was treated with K2[S2C@C(CN)2] (83 mg, 0.38 mmol) and
stirred for 2 h at r.t. The solution was filtered and the filtrate was
worked up as described for 15a.
3.21. Preparation of 17a with 5a or 7a as starting material
(a) A solution of 5a (102 mg, 0.27 mmol) in 25 ml of CH2Cl2 was
treated with C2(CN)4 (35 mg, 0.27 mmol) and stirred for 1 h at r.t.
The solution was filtered and the filtrate was worked up as de-
scribed for 15a; yield 90 mg (81%). (b) A solution of 7a (115 mg,
0.24 mmol) in 25 ml of CH2Cl2 was stepwise treated with CH2(CN)2
(48 mg, 0.72 mmol) and NaOMe (39 mg, 0.72 mmol). After the
reaction mixture was stirred for 24 h at r.t., it was filtered and
the filtrate was worked up as described for 15a; yield 76 mg (77%).
16a: Red violet solid; yield 36 mg (56%), m.p. 266 °C (dec.). Anal.
Calc. for C12H14CoN2PS2: C, 42.35; H, 4.15; N, 9.21; S, 18.85; Co,
17.32. Found: C, 42.41; H, 4.01; N, 9.42; S, 18.58; Co, 17.53%. MS
(70 eV) m/z 340 (M+), 200 (C5H5Co(PMe3)+). IR (KBr):
m(C„N)
2200, m
(C@N) 1405 cmꢀ1. UV (CH2Cl2, 10ꢀ6 mol/l): k = 513 nm. 1H
NMR (CDCl3, 90 MHz): d 5.10 (s, 5H, C5H5), 1.75 [d, 2J(PH) = 10.8,
9H, PCH3]. 31P NMR [CDCl3, 36.2 MHz]: d 21.1 (s).
16b: Red violet solid; yield 59 mg (77%), m.p. 136 °C (dec.). Anal.
Calc. for C17H16CoN2PS2: C, 50.75; H, 4.01; N, 6.96; S, 15.94; Co,
14.65. Found: C, 50.17; H, 3.93; N, 6.88; S, 16.02; Co, 14.25%. IR
3.22. Preparation of [(C5H5)Co(PMe3){Se2C@C(CN)2}] (18a)
This compound was prepared as described for 15a, with 118 mg
(0.26 mmol) of 1a and 162 mg (0.52 mmol) of K2[Se2C@C(CN)2] as
starting materials. Dark brown solid, yield 71 mg (63%); m.p.
176 °C (dec.). Anal. Calc. for C12H14CoN2PSe2: C, 33.20; H, 3.25; N,
6.45; Co, 13.58. Found: C, 32.96; H, 3.11; N, 6.18; Co, 13.31%. MS
(70 eV) m/z 436 (M+), 280 (M+ꢀSeC2(CN)2), 200 (C5H5Co(PMe3)+).
(KBr): m(C„N) 2200, m
(C@N) 1410 cmꢀ1. UV (CH2Cl2, 10ꢀ6 mol/l):
k = 519 nm. 1H NMR (CDCl3, 90 MHz): d 7.41–7.62 (br m, 5H,
C6H5), 4.94 (s, 5H, C5H5), 1.81 [d, 2J(PH) = 10.8, 6H, PCH3]. 31P
NMR [CDCl3, 36.2 MHz]: d 25.6 (s).
16c: Dark violet solid; yield 70 mg (79%), m.p. 206 °C (dec.).
Anal. Calc. for C22H18CoN2PS2: C, 56.89; H, 3.91; N, 6.03; S, 13.81;
Co, 12.69. Found: C, 56.90; H, 3.97; N, 5.84; S, 13.68; Co, 12.49%.
IR (KBr): m(C„N) 2200, m
(C@N) 1405 cmꢀ1. UV (CH2Cl2, 10ꢀ6 mol/
l): k = 534 nm. 1H NMR (CDCl3, 90 MHz): d 5.07 (s, 5H, C5H5),
1.73 [d, 2J(PH) = 10.6, 9H, PCH3]. 31P NMR [CDCl3, 36.2 MHz]: d
17.3 (s).
IR (KBr): m(C„N) 2200, m
(C@N) 1410 cmꢀ1. UV (CH2Cl2, 10ꢀ6 mol/
l): k = 530 nm. 1H NMR (CDCl3, 90 MHz): d 7.39–7.80 (br m, 10H,
C6H5), 5.00 (s, 5H, C5H5), 1.92 [d, 2J(PH) = 10.6, 3H, PCH3]. 31P
NMR [CDCl3, 36.2 MHz]: d 37.1 (s).
3.23. Preparation of [(C5Me5)Co(PMe3){Se2C@C(CN)2}] (18b)
16d: Red solid; yield 62 mg (62%), m.p. 206 °C (dec.). Anal. Calc.
for C27H20CoN2PS2: C, 61.59; H, 3.83; N, 5.32; S, 12.18; Co, 11.19.
Found: C, 61.51; H, 3.79; N, 5.56; S, 12.11; Co, 11.28%. IR (KBr):
This compound was prepared as described for 15a, with 136 mg
(0.26 mmol) of 3a and 162 mg (0.52 mmol) of K2[Se2C@C(CN)2] as
starting materials. Brown solid, yield 93 mg (71%); m.p. 113 °C
m
(C„N) 2200, m .
(C@N) 1410 cmꢀ1 UV (CH2Cl2, 10ꢀ6 mol/l):

22
H. Werner, L. Scheller / Polyhedron 34 (2012) 13–23
(dec.). Anal. Calc. for C17H24CoN2PSe2: C, 40.50; H, 4.80; N, 5.56; Co,
50.72; H, 4.68; S, 13.54; Rh, 14.48. Found: C, 50.14; H, 4.51; S,
11.69. Found: C, 40.22; H, 4.55; N, 5.19; Co, 11.73%. IR (KBr):
13.16; Rh, 14.24%. IR (KBr): m . UV (CH2Cl2,
(C@S) 990 cmꢀ1
m(C„N) 2200,
m
(C@N) 1400 cmꢀ1
.
UV (CH2Cl2, 10ꢀ6 mol/l):
10ꢀ6 mol/l): k = 488 nm. 1H NMR (CDCl3, 90 MHz): d 7.53–7.91
(br m, 15H, C6H5), 2.39 (s, 3H, SCH3), 1.60 [dd, 3J(RhH) = 0.4,
4J(PH) = 3.3, 15H, C5Me5]. 31P NMR (CDCl3, 36.2 MHz): d 38.4 [d,
1J(RhP) = 142.2].
k = 524 nm. 1H NMR (CDCl3, 90 MHz): d 1.62 [d, 4J(PH) = 1.6, 15H,
C5Me5], 1.55 [d, 2J(PH) = 9.7, 9H, PCH3]. 31P NMR [CDCl3,
36.2 MHz]: d 13.3 (s).
24: Yellow-green solid, yield 79 mg (79%), m.p. 144 °C (dec.),
3.24. Preparation of [(C5H5)Rh(PiPr3)(S2C@S)] (20a)
K X
= 77 cm2 ꢀ1 molꢀ1. Anal. Calc. for C16H19BF4IrPS3: C, 30.62; H,
4.66; S, 15.33. Found: C, 30.40; H, 4.91; S, 15.36%. IR (KBr):
A solution of 19a (120 mg, 0.30 mmol) in 25 ml of CH2Cl2 was
treated with K2CS3 (61 mg, 0.33 mmol) and stirred for 24 h at r.t.
The solution was filtered and the filtrate was worked-up as de-
scribed for 16a. Orange-yellow solid; yield 77 mg (59%), m.p.
79 °C (dec.). Anal. Calc. for C15H26PRhS3: C, 41.28; H, 6.00; S,
22.04; Rh, 23.58. Found: C, 41.47; H, 5.86; S, 22.29; Rh, 23.13%.
m
(C@S) 995 cmꢀ1. UV (CH2Cl2, 10ꢀ6 mol/l): k = 483 nm. 1H NMR
(CD3NO2, 90 MHz): d 6.04 [d, 3J(PH) = 1.1, 5H, C5H5], 2.76 (br m,
3H, PCH), 2.70 (s, 3H, SCH3), 1.32 [dvt, N = 14.4, 3J(PH) = 7.2, 18H,
PCHCH3]. 31P NMR (CDCl3, 36.2 MHz): d 23.7 (s).
Cyclic voltammetry: In a glovebox [N(nBu)4]PF6 and the electro-
active species were placed into a thoroughly dried CV cell. At a high
purity argon line acetonitrile was added through a gastight syringe.
Then a platinum disk working electrode, a platinum wire counter
electrode, and a Hg/HgCl2 reference electrode were placed into
the solution. The cyclic voltammograms were recorded at scan
rates between 50 and 200 mV/s using different starting and
switching potentials. For the determination of the oxidation poten-
tials, ferrocene (E1/2 = +0.40 V versus SCE) [44] was added as the
internal standard. Cyclic voltammograms were recorded using a
Potentioscan Wenking POS 73 model of Bank Electronics with an
XY recorder as described by Feldmann and Koberstein [45].
IR (KBr): m
(C@S) 1030 cmꢀ1. UV (CH2Cl2, 10ꢀ6 mol/l): k = 470 nm.
1H NMR (CDCl3, 90 MHz): d 5.56 [dd, 2J(RhH) = 0.5, 3J(PH) = 1.8,
5H, C5H5], 2.35 (br m, 3H, PCH), 1.26 [dvt, N = 14.0, 3J(PH) = 7.0,
18H, PCHCH3]. 31P NMR (CDCl3, 36.2 MHz):
1J(RhP) = 143.6].
d
63.0 [d,
3.25. Preparation of [(C5Me5)Rh(PPh3)(S2C@S)] (20b)
This compound was prepared as described for 20a, with 171 mg
(0.30 mmol) of 19b and 61 mg (0.33 mmol) of K2CS3 as starting
materials; reaction time 18 h. Orange-yellow solid, yield 115 mg
(63%); m.p. 201 °C (dec.). Anal. Calc. for C29H30PRhS3: C, 57.23; H,
4.97; S, 15.81; Rh, 16.91. Found: C, 56.61; H, 5.13; S, 15.52; Rh,
Acknowledgements
16.28%. IR (KBr):
m
(C@S) 1035 cmꢀ1. UV (CH2Cl2, 10ꢀ6 mol/l):
We gratefully acknowledge financial support from the Deutsche
Forschungsgemeinschaft and the Fonds der Chemischen Industrie.
We also thank Mrs. R. Schedl and Mr. C.P. Kneis (DTA and elemen-
tal analyses) and Dr. G. Lange and Mr. F. Dadrich (mass spectra).
k = 472 nm. 1H NMR (CDCl3, 90 MHz): d 7.28–7.78 (br m, 15H,
C6H5), 1.47 [dd, 3J(RhH) = 0.5, 4J(PH) = 3.1, 15H, C5Me5]. 31P NMR
(CDCl3, 36.2 MHz): d 39.7 [d, 1J(RhP) = 151.8].
3.26. Preparation of [(C5H5)Ir(PiPr3)(S2C@S)] (22)
References
This compound was prepared as described for 20a, with 171 mg
(0.30 mmol) of 21 and 61 mg (0.33 mmol) of K2CS3 as starting
materials; reaction time 18 h. Yellow-green solid, yield 60 mg
(41%); m.p. 120 °C (dec.). Anal. Calc. for C15H26IrPS3: C, 34.20; H,
4.98; S, 18.26. Found: C, 34.00; H, 5.14; S, 18.01%. IR (KBr):
[1] (a) Reviews: H. Werner, Coord. Chem. Rev. 43 (1982) 165;
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m
(C@S) 1035 cmꢀ1. UV (CH2Cl2, 10ꢀ6 mol/l): k = 469 nm. 1H NMR
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(CDCl3, 90 MHz): d 5.59 [d, 3J(PH) = 1.2, 5H, C5H5], 2.52 (br m, 3H,
PCH), 1.25 [dvt, N = 14.0, 3J(PH) = 7.0, 18H, PCHCH3]. 31P NMR
(CDCl3, 36.2 MHz): d 20.3 (s).
3.27. General procedure for the preparation of
[(C5R5)Rh(PR3)(S2CSMe)BF4 (23a, 23b) and
[(C5H5)Ir(PiPr3)(S2CSMe)BF4 (24)
A solution of 20a (87 mg, 0.20 mmol), 20b (122 mg, 0.20 mmol)
or 22 (84 mg, 0.16 mmol) in 30 ml of CH2Cl2 was treated under
stirring with an equimolar amount of [Me3O]BF4 (30 mg,
0.20 mmol or 24 mg 0.16 mmol, respectively) and continuously
stirred for 4 h at r.t. The solution was filtered and the filtrate was
brought to dryness in vacuo. The residue was washed three times
with 10 ml of diethyl ether and dried in vacuo.
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K
= 72 cm2 ꢀ1 molꢀ1. Anal. Calc. for C16H19BF4PRhS3: C, 35.74; H,
X
3.56; S, 17.89; Rh, 19.14. Found: C, 35.49; H, 3.38; S, 17.50; Rh,
18.99%. IR (KBr):
m .
(C@S) 995 cmꢀ1 UV (CH2Cl2, 10ꢀ6 mol/l):
k = 486 nm. 1H NMR (CD3NO2, 90 MHz): d 5.98 [dd, 2J(RhH) = 0.4,
3J(PH) = 1.5, 5H, C5H5], 2.78 (s, 3H, SCH3), 2.57 (br m, 3H, PCH),
1.34 [dvt, N = 14.2, 3J(PH) = 7.1, 18H, PCHCH3]. 31P NMR (CDCl3,
36.2 MHz): d 64.4 [d, 1J(RhP) = 131.0].
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K X
= 66 cm2 ꢀ1 molꢀ1. Anal. Calc. for C30H33PBF4PRhS3: C,

H. Werner, L. Scheller / Polyhedron 34 (2012) 13–23
23
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