Palladium(II) and platinum(II) complexes with bisphosphanes, [S 2C=C(CN)2]2- and [Se2C=C(CN) 2]2- as chelating ligands

Article abstract of DOI:10.1002/zaac.201100375

The palladium(II) and platin(II) 1, 1-dicyanoethylene-2, 2-dithiolates [(L-L)M{S₂C=C(CN)₂}] (M = Pd: L-L = dppm, dppe, dcpe, dpmb; M = Pt: dppe, dcpe, dpmb) were prepared either from[(L-L)MCl₂] and K₂[S₂C=C(CN)₂] or from [(PPh ₃)₂M{S₂C=C(CN)₂}] and the bisphosphane. Moreover, [(dppe)Pt{S₂C=C(CN)₂}]was obtained from [(1, 5-C₈H₁₂)Pt{S₂C=C(CN)₂}] and dppeby ligand exchange. The 1, 1-dicyanoethylene-2, 2-diselenolates[(dppe) M{Se₂C=C(CN)₂}] (M = Pd, Pt) were prepared from[(dppe)MCl₂] and K₂[Se₂C=C(CN) ₂]. The oxidation potentials of the square-planar palladium and platinum complexes were determined by cyclic voltammetry. The reaction of [(dcpe)Pd(S₂C=O)] with TCNE led to a ligand fragment exchange and gave the 1, 1-dicyanoethylene-2, 2-dithiolate [(dcpe)Pd{S₂C=C(CN) ₂}] in good yield. Copyright

Full text of DOI:10.1002/zaac.201100375

ARTICLE
DOI: 10.1002/zaac.201100375
Palladium(II) and Platinum(II) Complexes with Bisphosphanes,
[S2C=C(CN)2]2– and [Se2C=C(CN)2]2– as Chelating Ligands
Lothar Scheller[a] and Helmut Werner*[a]
Dedicated to Professor Wolfgang Beck on the Occasion of His 80th Birthday
Keywords: Chelate complexes; 1,1-Dicyanoethylene-2,2-dithiolate; 1,1-Dicyanoethylene-2,2-diselenolate; Palladium; Platinum
Abstract. The palladium(II) and platin(II) 1,1-dicyanoethylene-2,2-di-
[(dppe)M{Se2C=C(CN)2}] (M = Pd, Pt) were prepared from
thiolates [(L–L)M{S2C=C(CN)2}] (M = Pd: L–L = dppm, dppe, dcpe, [(dppe)MCl2] and K2[Se2C=C(CN)2]. The oxidation potentials of the
dpmb; M = Pt: dppe, dcpe, dpmb) were prepared either from square-planar palladium and platinum complexes were determined by
[(L–L)MCl2] and K2[S2C=C(CN)2] or from [(PPh3)2M{S2C=C(CN)2}] cyclic voltammetry. The reaction of [(dcpe)Pd(S2C=O)] with TCNE
and the bisphosphane. Moreover, [(dppe)Pt{S2C=C(CN)2}] led to a ligand fragment exchange and gave the 1,1-dicyanoethylene-
was obtained from [(1,5-C8H12)Pt{S2C=C(CN)2}] and dppe 2,2-dithiolate [(dcpe)Pd{S2C=C(CN)2}] in good yield.
by ligand exchange. The 1,1-dicyanoethylene-2,2-diselenolates
Introduction
Results and Discussion
In the context of our work on coordination compounds
formed from CS2 and related heteroallenes,[1] we found that
the palladium(0) complex [(PMe2Ph)2Pd(SCNPh)], formed
from [Pd(PMe2Ph]4 and SCNPh, reacted with a second mole-
cule of SCNPh to afford the palladium(II) derivative
[(PMe2Ph)2Pd(S2CNPh)] by elimination of CNPh[2]. Ana-
logues of [(PMe2Ph)2Pd(S2CNPh)] of the general composition
[(PR3)2M(S2CO)] and [(PR3)2Pd(S2CS)] (M = Pd, Pt) were
well known and had been prepared mainly from [(PR3)2MCl2]
and alkali salts of the anions [S2COMe]– or [S2CS]2–, respec-
tively.[3,4] The nickel complex [(dppe)Ni(S2CS)] was obtained
from [(dppe)Ni(chelate)] precursors and CS2 as source of the
trithiocarbonate ligand.[5]
The bisphosphane metal dichlorides 1a–1d and 2a–2c re-
acted with equimolar amounts of K2[S2C=C(CN)2] in
THF/CH2Cl2 at room temperature to give the four-coordinate
chelate complexes 3a–3d and 4a–4c in 70–78% isolated yield
(Scheme 1). An alternative procedure used the bis(triphenyl-
phosphane) palladium and platinum dichlorides 5 and 6 as
starting materials, which on treating with K2[S2C=C(CN)2] af-
forded the metal 1,1-dicyanoethylene-2,2-dithiolates 7 and 8.
The reactions of 7 with dppe and dpmb, and of 8 with dppe
readily led to the displacement of PPh3 and gave the chelate
complexes 3b, 3d and 4a. A similar substitution occurred on
treatment of 10 with dppe to furnish 4a (Scheme 2). In this
case, however, the reaction is slower than that of 8 with dppe.
The metal 1,1-dicyanoethylene-2,2-dithiolates 3a–3d,
4a–4c, 7 and 8 are yellow to orange, almost air-stable solids,
which are soluble in CH2Cl2 and chloroform, but insoluble in
hydrocarbons. Characteristic features of the IR spectra of
3a–3d, 4a–4c, 7 and 8 are the strong absorption at 2200–
2210 cm–1, corresponding to the CϵN stretching mode, and
The aim of the present study was firstly to prepare
a
series of palladium(II) and platinum(II) compounds
[(L–L)Pd(S2C=X)] and [(L–L)Pt(S2C=X)], where X is C(CN)2
instead of oxygen, sulfur, and NPh, and where L–L is a chelat-
ing bisphosphane such as dppe, dcpe etc. Secondly, we were
interested to find out whether the counterparts with
[Se2C=C(CN)2]2– as bidentate ligand were also accessible. We
point out that whereas some 1,1-dicyanoethylene-2,2-dithiolate the band at 1430–1435 cm–1, assigned to an olefinic C=C
stretch. Both numbers are in agreement with reference data.[3a]
The 31P NMR spectra of 3a–3d, 4a–4c, 7 and 8 display only
one signal, confirming the stereochemical equivalence of the
phosphane groups. From the satellites in the spectra of the
platinum complexes 4a–4c and 8, substantially large 195Pt–31P
coupling constants of 3000–3170 Hz could be determined. The
UV spectra of 3a–3d, 4a–4c, 7 and 8 show a maximum at
340–350 nm, which is at a similar position as found for the
palladium and platinum trithionates [(L–L)M(S2CS)] (L–L =
dppe, dcpe, dmpe).[8,9]
platinum(II)
complexes
[(L–L)Pt{S2C=C(CN)2]
with
1,1Ј-bis(diphenylphosphanyl)ferrocene,[6]
2,2-bipyridine,
1,10-phenanthroline and their derivatives were described,[7]
analogues with 1,1-dicyanoethylene-2,2-diselenolate as ligand,
to the best of our knowledge, were unknown.
* Prof. Dr. H. Werner
E-Mail: helmut.werner@mail.uni-wuerzburg.de
[a] Universität Würzburg
Anorganische Chemie
Am Hubland
97074 Würzburg, Germany
76
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2012, 638, (1), 76–80

PdII and PtII Complexes with [S2C=C(CN)2]2– and [Se2C=C(CN)2]2– as Ligands
dium–selenium single bonds; the Pd–Se distances in 11 being
quite similar to those in the maleonitrilediselenoate dianion
[Pd{Se2C2(CN)2}2]2–.[15] The C=C distances in 3b
(1.370(2) Å) and 11 (1.360(1) Å) are almost similar to those
in the structurally analogous platinum(II) complexes
[(1,5-C8H12)Pt{S2C=C(CN)CO2Et}]
[(PPh3)2Pt{S2C=CHC(O)Ph}]
(1.368(8) Å),[16]
(1.349(8) Å)[17]
and
[(PC16H13)2Pt{S2C=C(CO2Et)2}] (1.355(7) Å),[18] and corre-
spond to a carbon–carbon double bond. In the unit cell of 3b,
the molecules are not layered like in [Pd{S2C2(CN)2}2]2– and
[Pt{S2C2(CN)2}2]2–,[19] which is probably due to the spatial
arrangement of the PPh2 units. The Pd–Pd distances between
two neighboring molecules of 3b are larger than 6.0 Å and
thus exclude a direct metal–metal interaction as found in the
bis(maleonitrildithiolates).[20]
The oxidation chemistry of the palladium and the platinum
complexes 3b–3d, 7, 11 and 4a–4c, 8, 12 were investigated
both by electroanalytical and chemical studies. All complexes
showed irreversible oxidation waves in acetonitrile at room
temperature. As summarized in Table 1, the Epa values for the
1,1-dicyanoethylene-2,2-dithiolates are between 1.51 V and
1.64 V and depend only slightly on the phosphane ligand as
well as on the metal atom. The 1,1-dicyanoethylene-2,2-di-
selenolates 11 and 12 exhibit lower oxidation potentials than
their dithiolate counterparts 3b and 4a, which can be rational-
ized by the lower σ-donating capabilities of the dianion
[Se2C2(CN)2]2– compared with [S2C2(CN)2]2–. We note that
the Epa values of the dithiocarbonates [(dcpe)M(S2C=O)]
(M = Pd, Pt) are significantly lower than those of the analogues
3c and 4b,[9] which is in agreement with the substantial differ-
ence in the electronegativity of oxygen and the C(CN)2 frag-
ment.
Scheme 1. [(i) M = Pd: P–P = dppe. dpmb; M = Pt: P–P = dppe].
Scheme 2.
The preparation of the palladium(II) and platinum(II) 1,1-
dicyanoethylene-2,2-diselenolates 11 and 12 followed the same
route as used for 3b and 4a (Scheme 3). Similar to 3a–3d and
4a–4c, the diselenolates 11 and 12 are air-stable solids, the IR,
UV and 31P NMR spectra of which display only minor differ-
ences to those of the analogous metal 1,1-dicyanoethylene-2,2-
dithiolates.
Table 1. Oxidation Potentials of 1,1-dicyanoethylene-2,2-dithiolates
and 1,1-dicyanoethylene-2,2-diselenolates of palladium(II) and plati-
num(II) (in acetonitrile, referenced to the ferrocen/ferrocenium redox
couple).
Compd
Epa /VFc
compd
Epa /VFc
3b
3c
3d
4a
4b
+1.55
+1.58
+1.58
+1.64
+1.51
4c
7
8
11
12
+1.61
+1.60
+1.63
+1.33
+1.42
Attempts to oxidize the compounds 3b and 4a by chemical
means and trap the proposed paramagnetic cations
Scheme 3.
The X-ray diffraction analyses of 3b and 11 confirmed that [(dppe)M{S2C=C(CN)2}]+ in the presence of NH4[PF6] or
the two related complexes possess the proposed square-planar Na[BPh4] failed. The reaction of 3b with equimolar amounts
geometry. The bond angle S–Pd–S in 3b (74.7(1)°)[10] of chloroanil gave 1b as the main product, whereas on treat-
is considerably smaller than 90° but similar to that in ment of 3b with iodine the corresponding diiodide
[(PPh3)2Pd{S2C=C(CN)2}]
[(PMe2Ph)2Pd(S2CO)]
(S–Pd–S
(S–Pd–S
=
74.2(2)°),[11] [(dppe)PdI2] was obtained. The platinum complex 4a proved
=
75.4(1)°),[12] to be inert even in the presence of a tenfold excess of I2. Also
[(PPh3)2Pt(S2CO)] (S–Pt–S = 75.2(2)°),[3a] and analogous co- no reaction occurred upon treating 3b or 3c with tetracyano-
ordination compounds with trithiocarbonate as chelating li- ethylene (TCNE) as the electron acceptor. In contrast, the
gand.[13] The bond angle Se–Pd–Se in 11 is only slightly larger dithiocarbonato complex 13 reacted with TCNE in CH2Cl2 to
than in 3b and amounts to 77.61(4)°.[14] The Pd–S and Pd– give the 1,1-dicyanoethylene-2,2-dithiolate derivative 3c (see
Se distances (3b: 2.356(4) and 2.344(4) Å; 11: 2.425(1) and Scheme 4).
A
similar reaction occurred between
2.474(1) Å) are in the range of palladium–sulfur and palla- [(dcpe)Pd(S2CS)] and TCNE, although in this case side prod-
Z. Anorg. Allg. Chem. 2012, 76–80
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
77

L. Scheller, H. Werner
ARTICLE
K2[S2C=C(CN)2] (66 mg, 0.30 mmol) as starting materials. Pale yel-
low solid; yield 75 mg (75%); m.p. 266 °C (decomp.). IR (KBr): ν˜ =
2200 [ν (CN)], 1430 [ν (C=C)] cm–1. UV (CH2Cl2, 10–6 mol/L): λmax
= 340 nm. 31P NMR (36.2 MHz, CDCl3): δ = 81.4 (s) ppm.
C30H48N2P2PdS2 (669.2): calcd. C 53.84, H 7.23, N 4.19, S 9.58;
found C 53.57, H 7.11, N 4.20, S 9.50 %.
ucts were observed. We assume that the formation of 3c from
13 and TCNE proceeds by a [2+2] cycloaddition process via a
four-membered thietane intermediate. Such intermediates have
been observed in the reactions of [(C5Me5)Co(PMe3)-
(S2CS)] with TCNE,[9] and of thioketones and thioketenes with
electron poor olefins.[20]
Preparation of [(dpmb)Pd{S2C=C(CN)2}] (3d): (a) This compound
was prepared as described for 3a, with 1d (98 mg, 0.15 mmol) and
K2[S2C=C(CN)2] (66 mg, 0.30 mmol) as starting materials; yield
79 mg (73%). – (b) A solution of 7 (216 mg, 0.28 mmol) in CH2Cl2
(40 mL) was treated with dppe (132 mg, 0.28 mmol) and stirred for 4
h at room temperature. It was then worked up as described for (a).
Yellow solid; yield 179 mg (89%); m.p. 192 °C (decomp.). IR (KBr):
ν˜ = 2205 [ν (CN)], 1435 [ν (C=C)] cm–1. UV (CH2Cl2, 10–6 mol/L):
λmax = 343 nm. 1H NMR (90 MHz, CD2Cl2): δ = 7.35–7.70 (m, 24
H, C6H4 and C6H5), 3.80 (m, 4 H, CH2) ppm. 31P NMR (36.2 MHz,
CDCl3): δ = 15.6 (s) ppm. C36H28N2P2PdS2 (721.1): calcd. C 59.96,
H 3.91, N 3.88, S 8.89; found C 59.66, H 3.85, N 3.93, S 8.95 %.
Preparation of [(dppe)Pt{S2C=C(CN)2}] (4a): (a) This compound
was prepared as described for 3a, with 2a (100 mg, 0.15 mmol) and
K2[S2C=C(CN)2] (66 mg, 0.30 mmol) as starting materials; yield
86 mg (78%). – (b) A solution of 8 (241 mg, 0.28 mmol) in CH2Cl2
(40 mL) was treated with dppe (112 mg, 0.28 mmol) and stirred for 4
h at room temperature. It was then worked up as described for (a);
yield 177 mg (86%). – (c) A solution of 10 (102 mg, 0.23 mmol) in
CH2Cl2 (25 mL) was treated with dppe (92 mg, 0.23 mmol) and stirred
for 18 h at room temperature. Afterwards, it was worked up as de-
scribed for (a); yield 131 mg (88%); light yellow solid; yield 177 mg
(86%); m.p. 275 °C (decomp.). IR (KBr): ν˜ = 2205 [ν (CN)], 1430 [ν
(C=C)] cm–1. UV (CH2Cl2, 10–6 mol/L): λmax = 348 nm. 1H NMR
(90 MHz, CD2Cl2): δ = 7.39–7.89 (m, 20 H, C6H5), 2.52 (d, 4 H,
Scheme 4.
Experimental Section
General: All experiments were carried out under argon using Schlenk
techniques. The starting materials 1a–1d,[21] 2a–2c,[21,22] 5,[23] 6,[24]
9,[25] K2[S2C=C(CN)2],[26] K2[Se2C=C(CN)2][27] and K[S2COMe][28]
were prepared as described in the literature. NMR: Bruker WH 90,
JOEL FX 90Q. IR: Perkin–Elmer 397. UV: Hitachi 340. X-ray: Enraf
Nonius CAD4 diffractometer, MoKα radiation (0.70930 Å), graphite
monochromator, zirconium filter (factor 16.55). Melting points were
determined by DTA. Abbreviations used: dppm: CH2(PPh2)2;
3
2J(P,H) = 17.4, J(Pt,H) = 48.4 Hz, CH2) ppm. 31P NMR (36.2 MHz,
dppe:
1,2-C2H4(PPh2)2;
dcpe:
1,2-C2H4(PCy2)2;
dpmb:
CDCl3): δ = 41.3 (s, 2J(Pt,P) = 3058 Hz) ppm. C30H24N2P2PtS2 (733.7):
calcd. C 49.11, H 3.30, N 3.82, S 8.74; found C 49.23, H 3.49, N 3.67,
S 8.85 %.
1,2-C6H4(CH2PPh2)2; s: singlet; d: doublet; m: multiplet; br: broad
signal.
Preparation of [(dppm)Pd{S2C=C(CN)2}] (3a): A solution of 1a
(84 mg, 0.15 mmol) in THF/CH2Cl2 (1:3, 40 mL) was treated with
K2[S2C=C(CN)2] (66 mg, 0.30 mmol) and stirred for 1 h at room tem-
perature. The solution was filtered, and the filtrate was evaporated in
vacuo. An orange solid was obtained, which was washed three times
with hexane (5 mL) and dried; yield 66 mg (70%); m.p. 110 °C (de-
comp.). IR (KBr): ν˜ = 2205 [ν (CN)], 1430 [ν (C=C)] cm–1. UV
(CH2Cl2, 10–6 mol/L): λmax = 346 nm. 31P NMR (36.2 MHz, CDCl3):
δ = 30.4 (s) ppm. C29H22N2P2PdS2 (631.0): calcd. C 55.20, H 3.51, N
4.44, S 10.16; found C 55.12, H 3.50, N 4.32, S 10.32 %.
Preparation of [(dcpe)Pt{S2C=C(CN)2}] (4b): This compound was
prepared as described for 3a, with 2b (103 mg, 0.15 mmol) and
K2[S2C=C(CN)2] (66 mg, 0.30 mmol) as starting materials. Pale yel-
low solid; yield 86 mg (76%); m.p. 209 °C (decomp.). IR (KBr): ν˜ =
2200 [ν (CN)], 1430 [ν (C=C)] cm–1. UV (CH2Cl2, 10–6 mol/L): λmax
2
= 348 nm. 31P NMR (36.2 MHz, CDCl3): δ = 64.3 (s, J(Pt,P)
=
3005 Hz) ppm. C30H48N2P2PtS2 (757.9): calcd. C 47.54, H 6.38, N
3.70, S 8.46; found C 47.45, H 6.41, N 3.57, S 8.45 %.
Preparation of [(dpmb)Pt{S2C=C(CN)2}] (4c): This compound was
prepared as described for 3a, with 2c (111 mg, 0.15 mmol) and
K2[S2C=C(CN)2] (66 mg, 0.30 mmol) as starting materials; yield
79 mg (73%); pale yellow solid; yield 92 mg (76%); m.p. 214 °C (de-
comp.). IR (KBr): ν˜ = 2210 [ν (CN)], 1435 [ν (C=C)] cm–1. UV
Preparation of [(dppe)Pd{S2C=C(CN)2}] (3b): (a) This compound
was prepared as described for 3a, with 1b (86 mg, 0.15 mmol) and
K2[S2C=C(CN)2] (66 mg, 0.30 mmol) as starting materials; yield
75 mg (78%). – (b) A solution of 7 (216 mg, 0.28 mmol) in CH2Cl2
(40 mL) was treated with dppe (112 mg, 0.28 mmol) and stirred for 4
h at room temperature. It was then worked up as described for (a).
Bright yellow solid; yield 159 mg (88%); m.p. 170 °C (decomp.). IR
(KBr): ν˜ = 2205 [ν (CN)], 1430 [ν (C=C)] cm–1. UV (CH2Cl2, 10–6
1
(CH2Cl2, 10–6 mol/L): λmax = 349 nm. H NMR (90 MHz, CD2Cl2):
δ = 7.38–7.68 (m, 24 H, C6H4 and C6H5), 3.95 (m, 4 H, CH2) ppm.
2
31P NMR (36.2 MHz, CDCl3): δ = 0.6 (s, J(Pt,P) = 3083 Hz) ppm.
C36H28N2P2PtS2 (809.8): calcd. C 53.40, H 3.49, N 3.46, S 7.92; found
C 53.21, H 3.55, N 3.47, S 7.80 %.
1
mol/L): λmax = 342 nm. H NMR (90 MHz, CD2Cl2): δ = 7.48–7.82
(m, 20 H, C6H5), 2.59 (d, 4 H, 2J(P,H) = 20.5 Hz, CH2) ppm. 31P
NMR (36.2 MHz, CDCl3): δ = 54.5 (s) ppm. C30H24N2P2PdS2 (645.0):
calcd. C 55.86, H 3.75, N 4.34, S 9.94; found C 55.50, H 3.85, N 4.10,
S 9.79 %.
Preparation of [(PPh3)2Pd{S2C=C(CN)2}] (7): A solution of 5
(98 mg, 0.28 mmol) in THF/CH2Cl2 (1:3, 40 mL) was treated with
K2[S2C=C(CN)2] (33 mg, 0.15 mmol) and stirred for 2 h at 40 °C.
After the reaction mixture was cooled to room temperature, the solu-
Preparation of [(dcpe)Pd{S2C=C(CN)2}] (3c): This compound was tion was filtered, and the filtrate was evaporated in vacuo. An deep
prepared as described for 3a, with 1c (90 mg, 0.15 mmol) and yellow solid was obtained, which was washed three times with diethyl
78
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© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2012, 76–80

PdII and PtII Complexes with [S2C=C(CN)2]2– and [Se2C=C(CN)2]2– as Ligands
ether (5 mL) and dried; yield 84 mg (78%); m.p. 200 °C (decomp.).
which was dried in vacuo. The remaining pale yellow solid was char-
IR (KBr): ν˜ = 2210 [ν (CN)], 1430 [ν (C=C)] cm–1. UV (CH2Cl2, 10– acterized by IR and 31P NMR spectroscopy as 3c; yield 82 mg (72%).
6
1
mol/L): λmax = 346 nm. H NMR (90 MHz, CD2Cl2): δ = 7.20–7.55
(m, C6H5) ppm. 31P NMR (36.2 MHz, CDCl3): δ = 30.4 (s) ppm.
C40H30N2P2PdS2 (771.2): calcd. C 62.29, H 3.92, N 3.63, S 8.32;
found C 61.77, H 4.09, N 3.34, S 8.18 %.
Cyclic Voltammetry: In a glovebox [N(nBu)4]PF6 and the electroac-
tive 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 elec-
trode, and a Hg/HgCl2 reference electrode were placed into the solu-
tion. The cyclic voltammograms were recorded at scan rates between
50 and 200 mV·sec–1 using different starting and switching potentials.
Preparation of [(PPh3)2Pt{S2C=C(CN)2}] (8): This compound was
prepared as described for 7, with 6 (111 mg, 0.15 mmol) and
K2[S2C=C(CN)2] (33 mg, 0.15 mmol) as starting materials. Yellow so-
lid; yield 93 mg (76%); m.p. Ͼ300 °C. IR (KBr): ν˜ = 2210 [ν (CN)],
For the determination of the oxidation potentials, ferrocene (E1/2
=
+0.40 V vs. SCE) was added as the internal standard.[29] Cyclic vol-
tammograms were recorded using a Potentioscan Wenking POS 73
model of Bank Electronics with an XY recorder as described by Feld-
mann and Koberstein.[30]
1
1430 [ν (C=C)] cm–1. UV (CH2Cl2, 10–6 mol/L): λmax = 342 nm. H
NMR (90 MHz, CD2Cl2): δ = 7.18–7.57 (m, C6H5) ppm. 31P NMR
2
(36.2 MHz, CDCl3):
δ
=
17.0 (s, J(Pt,P)
=
3167 Hz) ppm.
C40H30N2P2PtS2 (859.9): calcd. S 7.46; found S 7.40 %.
Preparation of [(1,5-C8H12)Pt{S2C=C(CN)2}] (10): A suspension of
9 (123 mg, 0.33 mmol) and K2[S2C=C(CN)2] (87 mg, 0.40 mmol) in
CH2Cl2 (25 mL) was stirred for 12 h at 40 °C. After the reaction mix-
ture was cooled to room temperature, it was worked up as described
for 7; light yellow solid; yield 124 mg (85%); m.p. 210 °C (decomp.).
IR (KBr): ν˜ = 2215 [ν (CN)], 1430 [ν (C=C)] cm–1. UV (CH2Cl2, 10–
Acknowledgement
We gratefully acknowledge financial support from the Deutsche For-
schungsgemeinschaft and the Fonds der Chemischen Industrie. We
also thank Mrs R. Schedl and Mr C. P. Kneis (DTA and elemental
analyses) and Dr. G. Lange and Mr F. Dadrich (mass spectra).
6
1
mol/L): λmax = 338 nm. H NMR (90 MHz, CD2Cl2): δ = 5.64 (m,
4 H, CH=CH), 2.56 (br. m, 8 H, CH2) ppm. C12H12N2PtS2 (443.5):
calcd. C 32.50, H 2.73, N 6.32, S 14.46; found C 32.17, H 2.66, N
6.11, S 14.29 %.
References
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b) H. Werner, Angew. Chem. 1990, 102, 1109–1121; Angew.
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Preparation of [(dppe)Pd{Se2C=C(CN)2}] (11): This compound was
prepared as described for 3a, with 1b (104 mg, 0.18 mmol) and
K2[Se2C=C(CN)2] (112 mg, 0.36 mmol) as starting materials; reaction
time 2 h; orange brown solid; yield 94 mg (71%); m.p. 164 °C (de-
comp.). IR (KBr): ν˜ = 2200 [ν (CN)], 1430 [ν (C=C)] cm–1. UV
1
(CH2Cl2, 10–6 mol/L): λmax = 349 nm. H NMR (90 MHz, CD2Cl2):
2
δ = 7.33–7.62 (m, 20 H, C6H5), 2.56 (d, 4 H, J(P,H) = 20.5 Hz, CH2)
ppm. 31P NMR (36.2 MHz, CDCl3):
δ = 55.5 (s) ppm.
C30H24N2P2PdSe2 (738.8): calcd. C 48.77, H 3.27, N 3.79; found C
48.32, H 3.35, N 3.76 %.
Preparation of [(dppe)Pt{Se2C=C(CN)2}] (12): This compound was
prepared as described for 11, with 2a (120 mg, 0.18 mmol) and
K2[S2C=C(CN)2] (112 mg, 0.36 mmol) as starting materials; orange
brown solid; yield 104 mg (70%); m.p. 124 °C (decomp.). IR (KBr):
ν˜ = 2200 [ν (CN)], 1430 [ν (C=C)] cm–1. UV (CH2Cl2, 10–6 mol/L):
λmax = 354 nm. 1H NMR (90 MHz, CD2Cl2): δ = 7.40–7.88 (m, 20
H, C6H5), 2.47 (d, 4 H, 2J(P,H) = 17.6 Hz, CH2) ppm. 31P NMR
(36.2 MHz, CDCl3): δ = 43.4 (s) ppm. C30H24N2P2PtSe2 (827.5):
calcd. C 43.55, H 2.92, N 3.39; found C 43.26, H 2.94, N 3.57 %.
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with selected bond lengths and bond angles, the atomic param-
eters x, y, z, the isotropic temperature factors U(eq), and the aniso-
tropic temperature factors U11, U22, U33, U23, U13, U12 of 3b are
available by the corresponding author (H. W.) on request.
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Tables with selected bond lengths and bond angles, the atomic
parameters x, y, z, the isotropic temperature factors U(eq), and the
anisotropic temperature factors U11, U22, U33, U23, U13, U12 of 11
are available by the corresponding author (H. W.) on request.
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Preparation of [(dcpe)Pd(S2C=CO)] (13): A solution of 1c (102 mg,
0.17 mmol) in CH2Cl2 (30 mL) was treated with K[S2CCOMe]
(28 mg, 0.19 mmol) and stirred for 6 h at 40 °C. After the reaction
mixture was cooled to room temperature, it was worked up as de-
scribed for 7; pale yellow solid; yield 87 mg (82%); m.p. 234 °C
(decomp.). IR (KBr): ν˜ = 1600 [ν (CO)] cm–1. UV (CH2Cl2,
10–6 mol/L): λmax = 268 nm. 31P NMR (36.2 MHz, CDCl3): δ = 78.6
(s) ppm. C27H48OP2PdS2 (621.2): calcd. C 52.21, H 7.79, S 10.32;
found C 52.70, H 8.09, S 10.59 %.
Reaction of 13 with Tetracyanoethylene: A solution of 13 (106 mg,
0.17 mmol) in CH2Cl2 (20 mL) was treated with TCNE (26 mg,
0.20 mmol) and stirred for 48 h at room temperature. The solvent was
evaporated in vacuo, the residue was dissolved in CH2Cl2 (5 mL), and
the solution was chromatographed on Al2O3 (neutral, activity grade V,
height of column 5 cm). With CH2Cl2 a yellow fraction was eluted,
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Received: August 20, 2011
Online veröffentlicht: Dezember 6, 2011
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© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2012, 76–80