Differing coordination modes of (O-alkyl)-p-ethoxyphenyldithiophosphonato ligands in copper(I), silver(I) and gold(I) triphenylphosphine complexes

Article abstract of DOI:10.1002/zaac.200500356

The three (O-methyl)-p-ethoxyphenyldithiophosphonato triphenylphosphine complexes of copper, silver and gold, [(Ph₃P)_nM{S ₂P(OMe)C₆H₄OEt-p}] (M = Cu, n = 2; M = Ag, Au, n = 1) investigated structurally by X-ray diffraction exhibit remarkable structural differences. The copper compound is a four-coordinate chelate monomer with Cu-S 2.4417(6) and 2.5048(6) A; P-Cu-S 104.24(2)-114.01(2)°; Cu-S-P 82.49(3)° and 80.85(2)°. The silver compound is a cyclic dimer with bridging dithiophosphonato ligands and three-coordinate silver atoms [Ag-S 2.5371(5) and 2.6867(5) A; P-Ag-S 122.88(2)° and 122.17(2)°; Ag-S-P 89.32(2)° and 103.56(2)°]. The gold compound is monomeric with linear dicoordinate gold [Au-S 2.3218(6) A; P-Au-S 177.72(2)°, Au-S-P 100.97(3)°].

Full text of DOI:10.1002/zaac.200500356

DOI: 10.1002/zaac.200500356
Differing Coordination Modes of (O-Alkyl)-p-Ethoxyphenyldithiophosphonato
Ligands in Copper(I), Silver(I) and Gold(I) Triphenylphosphine Complexes
Ionel Haiduc*,a, Gellert Mezeia,b, Rodica Micu-Semeniuca, Frank T. Edelmann*,c, and Axel Fischerc
a Cluj-Napoca / Romania, Universitatea “Babes-Bolyai“, Facultatea de Chimie,
c Magdeburg, Germany, Otto-von-Guericke-Universität,Chemisches Institut
Received September 1st, 2005.
Dedicated to Professor Herbert W. Roesky on the Occasion of his 70th Birthday
Abstract. The three (O-methyl)-p-ethoxyphenyldithiophosphonato
triphenylphosphine complexes of copper, silver and gold,
[(Ph3P)nM{S2P(OMe)C6H4OEt-p}] (M ϭ Cu, n ϭ 2; M ϭ Ag, Au,
n ϭ 1) investigated structurally by X-ray diffraction exhibit remark-
able structural differences. The copper compound is a four-coordi-
phonato ligands and three-coordinate silver atoms [AgϪS
2.5371(5) and 2.6867(5) A; PϪAgϪS 122.88(2)° and 122.17(2)°;
˚
AgϪSϪP 89.32(2)° and 103.56(2)°]. The gold compound is mono-
˚
meric with linear dicoordinate gold [AuϪS 2.3218(6) A; PϪAuϪS
177.72(2)°, AuϪSϪP 100.97(3)°].
˚
nate chelate monomer with CuϪS 2.4417(6) and 2.5048(6) A;
PϪCuϪS 104.24(2)Ϫ114.01(2)°; CuϪSϪP 82.49(3)° and 80.85(2)°.
The silver compound is a cyclic dimer with bridging dithiophos-
Keywords: Copper; Silver; Gold; Dithiophosphonates; Phosphor-
1,1-dithiolates; Crystal structure
Introduction
in recent years it received due attention as a source of
(O-alkyl)aryldithiophosphonato ligands [9Ϫ11]. In most
cases the so-called Lawesson’s reagent [12], [p-Me-
OC6H4PS2]2, readily obtained from anisole and tetraphos-
phorus decasulfide, has been used. Alternatively, dithio-
phosphonato complexes can be prepared by the reaction of
Lawesson’s reagent with metal and non-metal alkoxides and
this procedure is best suited for the synthesis of main group
derivatives [13].
Phosphor-1,1-dithiolato ligands [1] are versatile metal com-
plex forming reagents and include O,O-dialkyl-dithiophos-
phates, (RO)2PS2Ϫ, dithiophosphinates, R2PS2Ϫ and the hy-
brid (O-alkyl)-aryldithiophosphonates, R(RЈO)PS2Ϫ. An
extensive coordination chemistry of dithiophosphates [2]
has been developed, but dithiophosphinates [3] received rel-
atively less attention, whereas dithiophosphonates have
been almost neglected until recently. This was mainly
caused by the differing availability of the ligands.
(O-alkyl)aryldithiophosphonato proligands can be con-
veniently prepared as dithiophosphonic acid O-monoesters
from the cyclic phosphine disulfide dimers (diphosphetane
disulfides), [RP(S)S]2, by ring cleavage with alcohols (under
anhydrous conditions). Although this reaction was known
for a long time [4] and some metal dithiophosphonato com-
plexes were investigated in various laboratories [5Ϫ8] only
Results
We report here some copper(I), silver(I) and gold(I) tri-
phenylphosphine complexes of [p-EtOC6H4P(ORЈ)S2]Ϫ li-
gands (RЈ ϭ Me, Et, iso-Pr) obtained from phenetole,
C6H5OC2H5. Introduction of a para-ethoxy substituent
improves the solubility of the derived metal complex
(O-alkyl)aryldithiophosphonates and facilitates their crys-
tallization from organic solvents. The derivatives with RЈ ϭ
Me have been investigated structurally by single crystal
X-ray diffraction and showed differing bonding modes of
the ligands. The copper(I) complex is a monomeric four-co-
ordinate chelate 1, containing an isobidentate (symmetrical)
dithiophosphonato ligand. Silver(I) forms a dimeric, eight-
membered ring, containing two bridging dithiophosphon-
ato ligands, 2. The gold(I) compound is again monomeric,
but with a monodentate (unsymmetrical) dithiophosphon-
ato ligand, with a long nonbonding intramolecular Au···S
distance (vide infra), 3.
* Prof. Dr. Ionel Haiduc
Facultatea de Chimie, Universitatea “Babes-Bolyai“,
Str. Arany Janos 11,
RO-3400 Cluj-Napoca, / Romania
E-mail: silazan@yahoo.com
* Prof. Dr. F. T. Edelmann
Chemisches Institut der Universität
D-39106 Magdeburg
E-mail: frank.edelmann@vst.uni-magdeburg.de
b) Present address: Department of Chemistry, University of Puerto
Rico, San Juan, PR 00931-3346, USA
Z. Anorg. Allg. Chem. 2006, 632, 295Ϫ300
© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
295

I. Haiduc, G. Mezei, R. Micu-Semeniuc, F. T. Edelmann, A. Fischer
The copper(I) complex, 1, R ϭ Me, was prepared by re-
acting [(Ph3P)2CuNO3], dissolved in nitrobenzene, with a
solution of (O-methyl)-p-ethoxyphenyldithiophosphonic
acid obtained in situ by dissolving the dimeric sulfide in
methanol. The ethyl (1, RЈ ϭ Et) and isopropyl (1, RЈ ϭ
iso-Pr) derivatives were obtained by reacting CuSO4·5H2O,
dissolved in methanol, with the ammonium salt
NH4[S2P(ORЈ)C6H4OEt-p] and triphenylphosphine, dis-
solved in ethanol. Similarly prepared were the silver com-
plexes, 2 (RЈ ϭ Me, Et, iso-PrO) by reacting AgNO3 and
PPh3 with the ammonium salts of the (O-alkyl)aryldithio-
phosphonic acid monoesters in methanolic solution. The
gold(I) compounds, 3 (RЈ ϭ Me, Et, iso-Pr) were obtained
from [(Ph3P)AuCl] and the ammonium salts in acetone
solution. In all cases the yields were good or very good (see
Experimental Part).
NMR spectra
Multinuclear (1H, 13C and 31P) NMR spectra of the metal
complexes were recorded, and the values of chemical shifts
and coupling constants are given in the Experimental Part.
1
In the H NMR spectra signals are observed in the fol-
lowing ranges: 1.1Ϫ1.5 ppm (OCH2CH3), 3.3Ϫ4.3 ppm (-
OCH2-), 6.7Ϫ6.9 ppm (meta-C6H4OEt), 7.8Ϫ8.1 ppm (or-
tho-C6H4OEt) and 7.1Ϫ7.6 (P-C6H5).
The 13C NMR spectra exhibit signals in the following
ranges: 14.6Ϫ16.4 ppm (OCH2CH3), 51.0Ϫ63.6 ppm (-OCH2),
113.4Ϫ113.8 ppm (meta-C6H4OEt), 128.1Ϫ134.3 ppm (ipso-
and ortho-C6H4OEt), and carbon atoms from metal coordi-
nated P(C6H5)3 (ipso, meta and para), 160.7Ϫ161.1 ppm
(para-C6H4OEt)
In the 31P NMR spectra the signals in the range
100Ϫ110 ppm were assigned to the dithiophosphonato li-
gand and those in the range Ϫ3 to Ϫ38 ppm to the coordi-
nated triphenylphosphine. Free triphenylphosphine displays
The new compounds were characterized by elemental
analysis, infrared and NMR spectra. For each of the three
metals one derivative has been subjected to single crystal
X-ray analysis.
a
31P chemical shift at Ϫ6 ppm. The 31P NMR shifts of
coordinated triphenylphosphine in the copper (Ϫ3 ppm),
silver (ϩ7 ppm) and gold (ϩ38 ppm) complexes are deter-
mined by the electron back donation from metal d-orbital
into vacant d-orbitals of phosphorus. In the case of the gold
compounds the shielding is more dramatic due to relativis-
tic effects.
Infrared spectra
The νsymPS2 and νasPS2 group frequencies of the new com-
pounds compared with those of the ammonium salt are
given in Table 1.
Table 1 Phosphorus-sulfur group vibration frequencies /cmϪ1 in 1Ϫ3
Compound
νsymPS2
νasPS2
Crystal structures
(Ph3P)2Cu[S2P(OMe)C6H4OEt-p] (1)
NH4[S2P(OMe)(C6H4OEt-p]
568
632
1, RЈ ϭ Me
1, RЈ ϭ Et
1, RЈ ϭ iso-Pr
520
519
518
643
642
642
Crystals of 1, RЈ ؍ Me, were obtained by layering an aceto-
nitrile solution with hexane. The crystal retains a molecule
of solvent which is lost on storage. The compound crys-
tallizes in the monoclinic space group P21/c and is mono-
meric. The molecular structure with the atomic numbering
scheme is shown in Fig. 1, and the parameters are listed in
Table 2. The compound contains a CuS2P four-membered
chelate ring, and the coordination geometry of copper is
basically tetrahedral, with a distortion caused by the small
bite of the PS2 group, S1ϪCuϪS2 84.(7)°. The ligand is
2, RЈ ϭ Me
2, RЈ ϭ Et
2, RЈ ϭ iso-Pr
520
520
518
650
650
650
3, RЈ ϭ Me
3, RЈ ϭ Et
510
512
647
648
The frequencies were assigned by comparison with litera-
ture data [8b, 14]. It is obvious that in a given series (Me/Et/
iso-Pr) the νasPS2 frequency is practically constant, whereas
νsymPS2 decrease with increasing size of the RЈ group, in
agreement with the inductive electron repulsion effects of
these groups.
˚
isobidentate, as shown by PϪS1 1.9933(8) A and P3ϪS2
˚
˚
1.9946(8) A and CuϪS1 2.4417(6) and CuϪS2 2.5048(6) A.
The CuϪP bonds differ only slightly with 2.2852(6) and
˚
2.2786(6) A.
296
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© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2006, 295Ϫ300

Copper(I), Silver(I) and Gold(I) Triphenylphosphine Complexes
Fig. 2 Molecular structure of compound 2
Fig. 1 Molecular structure of compound 1·MeCN
˚
Table 3 Bond lengths /A and angles /° for compound 2, RЈ ϭ Me
˚
AgϪP(1)
AgϪS(1)#1
AgϪS(2)
S(1)ϪP(2)
S(1)ϪAg#1
S(2)ϪP(2)
O(2)ϪC(23)
O(2)ϪC(26)
2.4314(5)
2.5371(5)
2.6867(5)
2.0199(7)
2.5371(5)
1.9890(7)
1.374(2)
P(1)ϪC(1)
P(1)ϪC(7)
P(1)ϪC(13)
P(2)ϪO(1)
P(2)ϪC(20)
O(1)ϪC(19)
O(1)ϪP(2)ϪC(20)
O(1)ϪP(2)ϪS(2)
C(20)ϪP(2)ϪS(2)
O(1)ϪP(2)ϪS(1)
C(20)ϪP(2)ϪS(1)
S(2)ϪP(2)ϪS(1)
C(19)ϪO(1)ϪP(2)
C(23)ϪO(2)ϪC(26)
1.831(2)
1.832(2)
1.838(2)
1.6182(15)
1.806(2)
1.444(2)
97.33(8)
112.61(6)
112.32(7)
107.08(6)
112.36(7)
113.88(3)
119.96(12)
119.0(2)
Table 2 Bond lengths /A and angles /° for compound 1·MeCN,
RЈ ϭ Me
CuϪP(2)
CuϪP(1)
CuϪS(1)
CuϪS(2)
2.2786(6)
2.2852(6)
2.4417(6)
2.5048(6)
1.9933(8)
1.9946(8)
1.827(2)
1.829(2)
1.829(2)
1.824(2)
1.827(2)
1.830(2)
1.609(2)
1.800(2)
1.444(3)
1.366(3)
O(2)ϪC(64)
1.431(3)
124.68(2)
110.59(2)
114.01(2)
111.32(2)
104.24(2)
84.17(2)
82.49(3)
80.85(2)
105.79(7)
111.12(8)
112.22(7)
111.30(8)
112.49(3)
119.3(2)
117.0(2)
P(2)ϪCuϪP(1)
P(2)ϪCuϪS(1)
P(1)ϪCuϪS(1)
P(2)ϪCuϪS(2)
P(1)ϪCuϪS(2)
S(1)ϪCuϪS(2)
P(3)ϪS(1)ϪCu
P(3)ϪS(2)ϪCu
O(1)ϪP(3)ϪS(1)
C(58)ϪP(3)ϪS(1)
O(1)ϪP(3)ϪS(2)
C(58)ϪP(3)ϪS(2)
S(1)ϪP(3)ϪS(2)
C(57)ϪO(1)ϪP(3)
C(61)ϪO(2)ϪC(64)
1.426(3)
S(1)ϪP(3)
S(2)ϪP(3)
P(1)ϪC(11)
P(1)ϪC(21)
P(1)ϪC(1)
P(2)ϪC(31)
P(2)ϪC(41)
P(2)ϪC(51)
P(3)ϪO(1)
P(3)ϪC(58)
O(1)ϪC(57)
O(2)ϪC(61)
P(1)ϪAgϪS(1)#1
P(1)ϪAgϪS(2)
S(1)#1ϪAgϪS(2)
P(2)ϪS(1)ϪAg#1
P(2)ϪS(2)ϪAg
132.88(2)
122.17(2)
98.01(2)
103.56(2)
89.32(2)
Symmetry transformations used to generate equivalent atoms:
#1 Ϫxϩ1,Ϫy,Ϫzϩ1
[(Ph3P)Au{S2P(OMe)C6H4OEt-p}]
Crystals of compound 3, RЈ ϭ Me, were obtained directly
from the synthesis and belong to the monoclinic space
group P21/c. The compound is monomeric. The molecular
structure with the atom numbering scheme is shown in Fig-
ure 3, and the structural parameters are listed in Table 4.
The gold atom is dicoordinate with a nearly linear arrange-
ment: P1ϪAuϪS1 177.72(2)°. The AuϪP bond length is
[(Ph3P)Ag{S2P(OMe)C6H4OEt-p}]
Single crystals of 2, RЈ ؍ Me, were grown from dichloro-
methane layered with hexane. The compound crystallizes in
¯
the triclinic space group P1 and is a centrosymmetric dimer
˚
based upon an eight-membered Ag2S4P2 ring formed via
bridging coordination of the ligands. The molecular struc-
ture with the atom numbering scheme is shown in Figure 2,
and the structural parameters are listed in Table 3. The sil-
ver atoms are trigonally coordinated. The AgϪS bond
2.2599(6) A, shorter than the AgϪP bond in 2, RЈ ϭ Me,
and even the CuϪP bond in 1, RЈ ϭ Me, due to relativistic
effects which enhance the AuϪP bond strength, as sug-
gested also by the 31P NMR spectra. The primary AuϪS
˚
bond is 2.3218(6) A, again shorter than the CuϪS and
˚
lengths differ slightly, AgϪS2 2.6867 (5) A and AgϪS1#
AgϪS bonds in 1 and 2, RЈ ϭ Me. The second sulfur atom
˚
˚
2.5371(5) A, as well as the PϪS bonds, P2ϪS1 2.0199(7) A
is far from the metal atom and the Au···S distance of
˚
˚
and P2ϪS1 1.9890(7) A, suggesting that one of the PϪS
3.645 A is too large even for a secondary gold-sulfur bond.
bonds retains some double bond character. The AgϪP1
bond length is 2.4314(5) A, longer than the CuϪP bond
length measured in 1, RЈ ϭ Me.
Therefore, the dithiophosphonato ligand is monodentate,
˚
˚
with P2ϪS1 2.0606(9) A (single PϪS bond) and P2ϪS2
˚
1.9510(9) A (double PϭS bond).
Z. Anorg. Allg. Chem. 2006, 295Ϫ300
© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
zaac.wiley-vch.de
297

I. Haiduc, G. Mezei, R. Micu-Semeniuc, F. T. Edelmann, A. Fischer
cedures. Solvents were purified and dried by standard techniques
[19]. Elemental analyses were performed on a LECO CHNS-932
analyzer. Infrared and NMR spectra were recorded on Perkin
Elmer 2000 FT-IR and Bruker DPX-400 instruments, respectively.
Melting points were measured on an Electrothermal IA9100 appar-
atus and are reported without correction.
No intermolecular aurophilic interactions were observed
in the crystal, the shortest Au···Au distance being very large
˚
˚
(6.548 A). The intermolecular Au···S distances of 3.8670 A
are also too large for a secondary bond interaction, since
the sum of the van der Waals radii for the Au/S pair is
˚
3.50 A.
Syntheses
NH4[S2P(OMe)C6H4OEt-p]: 7.92 g of [S(S)PC6H4OEt-p]2 were ad-
ded to a mixture of 50 ml anhydrous benzene and 1.8 ml anhydrous
methanol. After stirring for 30 minutes at 40 Ϫ 60 °C, the solid
dissolved and a clear, colourless solution was obtained. Excess dry
NH3 was bubbled through the ice-cooled solution, giving rise to a
voluminous, white precipitate. The thick slurry was taken up into
50 ml anhydrous benzene, filtered, washed with benzene and dried
in a vacuum dessicator. Yield: 9.47 g (97 %). Mp 152 Ϫ 158 °C
(decomp.). For C9H16NO2PS2, calcd.: C 40.74, H 6.08, N 5.28;
found C 40.54, H 6.53, N 5.43 %. NH4[S2P(OMe)C6H4OEt-p] is a
white, non-hygroscopic powder, which is soluble in H2O, alcohols,
acetone, MeCN, THF and insoluble in benzene, Et2O, CH2Cl2,
CHCl3, CCl4.
Fig. 3 Molecular structure of compound 3
˚
Table 4 Bond lengths /A and angles /° for compound 3, RЈ ϭ Me
NH4[S2P(OEt)C6H4OEt-p]:
A similar procedure using 6.25 g
AuϪP(1)
AuϪS(1)
2.2599(6)
2.3218(6)
3.8670(7)
2.0606(9)
1.9510(9)
1.607(2)
1.433(3)
1.356(3)
1.434(3)
P(2)ϪS(1)ϪAu
100.97(3)
112.79(8)
114.62(8)
113.94(8)
98.27(10)
112.19(8)
114.60(9)
106.48(8)
105.39(8)
117.83(4)
119.6(2)
[S(S)PC6H4OEt-p]2 and 2.0 ml anhydrous EtOH. Yield: 7.43 g
(92 %). Mp 157 Ϫ 160 °C (decomp.). For C10H18NO2PS2, calcd.:
C 42.99, H 6.49, N 5.01; found C 42.67, H 6.11, N 5.07 %.
C(1)ϪP(1)ϪAu
C(13)ϪP(1)ϪAu
C(7)ϪP(1)ϪAu
O(1)ϪP(2)ϪC(20)
O(1)ϪP(2)ϪS(2)
C(20)ϪP(2)ϪS(2)
O(1)ϪP(2)ϪS(1)
C(20)ϪP(2)ϪS(1)
S(2)ϪP(2)ϪS(1)
C(19)ϪO(1)ϪP(2)
C(23)ϪO(2)ϪC(26)
AuϪS(2)#1
S(1)ϪP(2)
S(2)ϪP(2)
P(2)ϪO(1)
O(1)ϪC(19)
O(2)ϪC(23)
O(2)ϪC(26)
NH4[S2P(OPri)C6H4OEt-p]: A similar procedure using 7.23 g
[S(S)PC6H4OEt-p]2 and 2.8 ml anhydrous PriOH. Yield: 9.34 g
(95 %). Mp 166 Ϫ 169 °C (decomp.). For C11H20NO2PS2, calcd.:
C 45.03, H 6.87, N 4.77; found C 44.51, H 7.35, N 4.78 %.
P(1)ϪAuϪS(1)
P(1)ϪAuϪS(2)#1
S(1)ϪAuϪS(2)#1
177.72(2)
97.11(2)
82.27(2)
118.2(2)
[(Ph3P)2Cu{S2P(OMe)C6H4OEt-p}]: The free acid HS(S)P(OMe)-
C6H4OEt-p was prepared in a 100 ml flask by dissolving 2.16 g of
the disulfide [S(S)P(OMe)C6H4OEt-p]2 in 40 ml anhydrous meth-
anol under mild heating. The clear solution was treated with 3.25 g
(Ph3P)2CuNO3 and 20 ml nitrobenzene and the solution was re-
fluxed for 30 minutes. The crystalline white precipitate which sepa-
rated on cooling was filtered, washed with methanol and dried in va-
cuo. Yield 3.48 g (83 %), m.p. 182 °C (decomp). C45H42O2P3S2Cu,
calcd.: C 64.69; H 5.07, S 7.68; found C 64.66, H 5.66; S 7.67 %.
Symmetry transformations used to generate equivalent atoms:
#1 x,Ϫyϩ1/2,zϩ1/2
Conclusions
The three related compounds [(Ph3P)nM{S2P(OMe)-
C6H4OEt-p}] of copper (n ϭ 2), silver (n ϭ 1) and gold
(n ϭ 1) investigated structurally by X-ray diffraction exhibit
remarkable structural differences. The metals are: four-
coordinate tetrahedral in monomeric 1 (M ϭ Cu), tri-
coordinate trigonal planar in dimeric 2 (M ϭ Ag) and di-
coordinate linear in monomeric 3 (M ϭ Au), reflecting dif-
ferent bonding properties, enhanced by the relativistic ef-
fects in the case of gold. Similar contrasting bonding modes
in the Cu(I)ϪAg(I)ϪAu(I) triad were reported in the
triphenylphosphine metal complexes of these metals with
another dithioligand, namely dithiotetraphenylimidodi-
phosphinato anion, [SPPh2NPPh2S]Ϫ, and the difference is
supported by DFT calculations for these compounds [15].
1H NMR: OCH2CH3 1.41 t, 3H, 3J(HH) 7.0 Hz; P-OCH3 3.36 d, 3H, 3J(PH)
15.1 Hz; OCH2 4.04 q, 2H, 3J(HH) 7.0 Hz; meta-C6H4OEt 6.76 dd, 2H,
3J(HH) 8.8 Hz, 4J(PH) 2.7 Hz; ortho-C6H4OEt 7.82 dd, 2H, 3J(HH) 8.8 Hz,
3J(PH) 14.2 Hz; CuP-C6H5 7.11Ϫ7.37 m, 30 H. 13C NMR: OCH2CH3
14.73 s, P-OCH3 51.01 d, 2J(PC) 6.6 Hz, OCH2 63.44 s, meta-C6H4OEt
113.46 d, 3J(PC) 15.4 Hz, ortho-C6H4OEt 131.56 d, 2J(PC) 14.2 Hz, para-
C6H4OEt 131.56 d, 2J(PC) 14.2 Hz, CuP-C6H5 meta 128.19 d, 3J(PC) 8.6 Hz,
para 129.26 s, ortho 133.91 d, 2J(PC) 14.1 Hz; para-C6H4OEt 160.70 d,
4J(PC) 2.9 Hz. 31P NMR: PPh3 Ϫ3.01s, PS2 100.88 s, 3J(HP) 14.5 Hz.
[(Ph3P)2Cu{S2P(OEt)C6H4OEt-p}]: An amount of 0.3 g
CuSO4·5H2O was dissolved in 10 ml methanol. To this solution
was added dropwise, under stirring, a solution obtained by dissolv-
ing 0.67 g NH4[S2P(OEt)C6H4OEt-p] and 0.63 g PPh3 in 20 ml of
hot ethanol. The mixture was stirred for 15 minute and the white
precipitate formed was filtered, washed with methanol, water and
finally with petroleum ether and was dried in vacuo over CaCl2.
Yield 0.84 g (82 %), m.p. 147Ϫ153 °C; decomp. ca. 170 °C.
Experimental Part
[(Ph3P)2Cu{S2P(OPri)C6H4OEt-p}]: The compound was similarly
prepared from 0.3 g CuSO4·5H2O, 0.70 g NH4[S2P(OPri)C6H4OEt-p]
and 0.63 g PPh3. The viscous mass formed solidified on standing
and cooling, Yield 0.86 g (83 %), m.p. 130Ϫ135 °C (decomp).
All commercially available reagents were used as received. Some,
including [S(S)PC6H4OEt-p]2 [16], [(Ph3P)2CuNO3] [17], and
[(Ph3P)AuCl] [18] were prepared according to published pro-
298
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© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2006, 295Ϫ300

Copper(I), Silver(I) and Gold(I) Triphenylphosphine Complexes
[(Ph3P)Ag{S2P(OMe)C6H4OEt-p}]: A solution of 0.5 g AgNO3
and 0.77 g PPh3 in 40 ml methanol was treated dropwise under
stirring with a solution of 0.78 g NH4[S2P(OMe)C6H4OEt-p] in
5 ml methanol. The white precipitate formed was filtered after 15
minutes of stirring and washed with methanol and ether and dried.
Yield 1.76 g (97 %), m.p. 182Ϫ184 °C (decomp.). C27H27O2P2S2Ag,
calcd: C 52.52, H 4.41, S 10.39; found: C 52.35, H 4.63, S 10.17 %.
[(Ph3P)Au{S2P(OMe)C6H4OEt-p}]: A solution of 0.2 g (Ph3P)AuCl
in 10 ml acetone was tretaed with a solution of 0.11 g NH4[S2P(OMe)-
C6H4OEt-p] in 5 ml acetone. The white precipitate of NH4Cl was
filtered and the clear filtrate was left in the refrigerator. The white,
shiny crystals formed were filtered and washed with a small amount
of acetone and dried in air. Yield 0.25 g (88 %), m.p. 114Ϫ116 °C,
decomp. 170 °C. C27H27O2P2S2Au, calcd.: 45.90, H 3.85, S 9.08;
found: 46.14, H 4.26, S 9.05 %.
1H NMR (ppm): OCH2CH3 1.37 t, 3H, 3J(HH) 7.0 Hz; P-OCH3 3.49 d, 3H,
3J(PH) 15.1 Hz; OCH2 3.96 q, 2H, 3J(HH) 7.0 Hz; meta-C6H4OEt 6.70 dd,
2H, 3J(HH) 8.7 Hz, 4J(PH) 2.8 Hz; ortho-C6H4OEt 7.90 dd, 2H, 3J(HH)
8.7 Hz, 3J(PH) 13.8 Hz; P-C6H5 7.24Ϫ7.43 m, 30 H;
1H NMR (ppm): OCH2CH3 1.40 t, 3H, 3J(HH) 7.0 Hz; P-OCH3 3.84 d, 3H,
3J(PH) 15.3 Hz; OCH2 4.02 q, 2H, 3J(HH) 7.0 Hz; meta-C6H4OEt 6.83 dd,
2H, 3J(HH) 8.9 Hz, 4J(PH) 2.8 Hz; ortho-C6H4OEt 8.07 dd, 2H, 3J(HH)
8.9 Hz, 3J(PH) 13.9 Hz; AuP-C6H5 7.41Ϫ7.54 m, 30 H; 13C NMR:
OCH2CH3 14.67 s; P-OCH3, 51.45 d, 2J(PC) 6.7 Hz; OCH2 63.44 s; meta-
C6H4OEt 113.69d, 3J(PC) 15.5 Hz; ortho-C6H4OEt 131.92 d, 2J(PC)
13.6 Hz; para-C6H4OEt 161.04 d, 4J(PC) 3.3 Hz; ipso-C6H4OEt 133.06 d,
1J(PC) 120.4 Hz; AuP-C6H5 meta 129.11 d, 3J(PC) 11.7 Hz, para 131.68 s,
ortho 134.14 d, 2J(PC) 13.9 Hz, ipso 129.08 d, 2J(PC) 58.5 Hz; 31P NMR:
PPh3 38.01 s; PS2 104.50 s, 3J(HP) 14.7 Hz.
13C NMR: OCH2CH3 14.69 s; P-OCH3 52.02 d, 2J(PC) 7.3 Hz; OCH2
63.37 s; meta-C6H4OEt 113.52 d, 3J(PC) 15.3 Hz; ortho-C6H4OEt 132.10 d,
2J(PC) 14.2 Hz; ipso-C6H4OEt 131.24 d, 1J(PC) 114.4 Hz; AgP-C6H5 meta
128.62 d, 3J(PC) 8.6 Hz, para 129.93 s, ortho 134.03 d, 2J(PC) 16.3 Hz, ipso
132.48 d, 2J(PC) 26.2 Hz; para-C6H4OEt 160.86 d, 4J(PC) 3.1 Hz;
31P NMR: PPh3 7.50 s, PS2 110.49 s, 3J(HP) 14.6 Hz.
[(Ph3P)Ag{S2P(OEt)C6H4OEt-p}]: The compound was similarly
prepared from 0.3 g AgNO3, 0.49 g NH4[S2P(OEt)C6H4OEt-p] and
0.46 g PPh3. Yield 1.03 g (93 %), m.p. 140Ϫ143 °C (decomp.).
[(Ph3P)Au{S2P(OEt)C6H4OEt-p}]: The compound was similarly
prepared from 0.2 g (Ph3P)AuCl, 0.13 g NH4[S2P(OMe)-
C6H4OEt-p]. Yield 0.24 g (83 %), mp. 106Ϫ108 °C, decomp.
165 °C. C28H29O2P2S2Au, calcd.: C 46.67, H 4.06, S 8.90; found: C
46.14, H 4.37, S 8.74 %.
1H NMR (ppm): POCH2CH3 1.11 t, 6H, 3J(HH) 7.0 Hz; C6H4-OCH2CH3
1.39 t, 6H, 3J(HH) 6.9 Hz; C6H4OCH2CH3 and POCH2CH3 3.95 m, 4H,
4H; meta-C6H4OEt 6.71 dd, 4H, 3J(HH) 8.6 Hz, 4J(PH) 2.7 Hz; ortho-
C6H4OEt 7.94 dd, 4H, 3J(HH) 8.8 Hz, 3J(PH) 13.8 Hz; AgP-C6H5
7.25Ϫ7.45 m, 30H. 13C NMR: C6H4OCH2CH3 14.82 s; P-OCH2CH3
16.21 d, 2J(PC) 9.5 Hz; P-OCH2CH3 61.74 d, 2J(PC) 6.7 Hz;
C6H4OCH2CH3 63.45 s; meta-C6H4OEt 113.57 d, 3J(PC) 15.1 Hz; ortho-
C6H4OEt 132.16 d, 2J(PC) 13.9 Hz; ipso-C6H4OEt 131.90 d, 1J(PC)
114.4 Hz; AgP-C6H5 ortho 134.14 d, 2J(PC) 16.4 Hz, ipso 132.60 d, 2J(PC)
25.3 Hz; para-C6H4OEt 160.87 s 31P NMR: PPh3 6.96 s, PS2 107.32 s.
1H NMR (ppm): POCH2CH3 1.34 t, 3H, 3J(HH) 6.9 Hz; C6H4OCH2CH3
1.40 t, 3H, 3J(HH) 6.8 Hz; C6H4OCH2CH3 4.02 q, 2H, 3J(HH) 6.7 Hz;
POCH2CH3 4.27 q, 2H, 3J(HH/PH) 7.5 Hz; meta-C6H4OEt 6.83 dd, 2H,
3J(HH) 7.9 Hz; AuP-C6H5 7.47Ϫ7.51 m, 30 H; ortho-C6H4OEt 8.08 dd, 2H,
3J(HH) 8.2 Hz, 3J(PH) 13.6 Hz; 13C NMR: C6H4OCH2CH3 14.82 s;
P-OCH2CH3, 16.39 d, 3J(PC) 8.9 Hz; POCH2CH3 61.16 s; C6H4OCH2CH3
63.55 s, meta-C6H4OEt 113.77 d, 3J(PC) 15.6 Hz; AuP(C6H5)3 para- and or-
tho, ipso-C6H4OEt 131.0Ϫ133.0 m, AuP-C6H5 meta 129.23 d, 3J(PC)
11.5 Hz, AuP-C6H5 ortho 134.26 d, 3J(PC) 14.1 Hz; 31P NMR: PPh3 38.00 s;
PS2 101.22 s.
[(Ph3P)Ag{S2P(OPri)C6H4OEt-p}]: The compound was similarly
prepared from 0.3 g AgNO3, 0.46 g PPh3 and 0.52 g NH4[S2P(OPri)-
C6H4OEt-p]. Yield 1.03 g (90 %), m.p. 165Ϫ168 °C (decomp.).
Table 5 Crystallographic data for compounds 1, 2 and 3.
1·MeCN
2
3
Empirical formula
Formula weight
Temperature /K
C47H45CuNO2P3S2
876.41
173(2)
C54H54Ag2O4P4S4
1234.83
173(2)
C27H27AuO2P2S2
706.51
173(2)
3
˚
Wavelength /A
Crystal system
Space group
0.71073
0.71073
0.71073
monoclinic
P21/c (No. 14)
13.0704(2)
27.7424(3)
12.7558(1)
90
109.471(1)
90
4360.79(9)
4
triclinic
monoclinic
P21/c (No. 14)
9.4323(1)
20.7062(1)
13.4458(2)
90
92.219(1)
90
2624.09(5)
4
¯
P1 (No. 2)
˚
a /A
10.8802(2)
11.8510(1)
12.7811(2)
113.595(1)
106.742(1)
99.148(1)
1373.76(4)
1
1.493
˚
b /A
˚
c /A
α /°
β /°
γ /°
3
˚
Volume /A
Z
Dcalc /g cmϪ3
1.335
0.745
1.788
5.911
μ /mmϪ1
1.024
F(000)
1824
628
1384
Crystal size /mm
θ range /°
Index ranges
0.65 ϫ 0.12 ϫ 0.06
1.47 Ϫ 28.29
Ϫ17 Յ h Յ 16
Ϫ14 Յ h Յ 12
Ϫ12 Յ h Յ 4
28966
10724 [R(int) ϭ 0.0354]
1.00 / 0.86
10723 / 0 / 508
1.090
0.45 ϫ 0.40 ϫ 0.10
1.89 Ϫ 28.26
Ϫ36 Յ k Յ 31
Ϫ15 Յ k Յ 12
Ϫ26 Յ k Յ 27
9172
6459 [R(int) ϭ 0.0189]
1.00 / 0.76
6450 / 0 / 309
1.018
0.50 ϫ 0.35 ϫ 0.30
1.81 Ϫ 28.28
Ϫ16 Յ l Յ 16
Ϫ8 Յ l Յ 17
Ϫ17 Յ l Յ 17
17339
6447 [R(int) ϭ 0.0235]
1.00 / 0.70
6441 / 0 / 309
1.084
Reflections collected
Unique reflections
Max. and min. transmission
Data/restraints/parameters
Goodness-of-fit
Final R indices
0.0405 / 0.0762
0.0276; 0.0687
0.0210; 0.0446
R1 / wR2 [I>2σ(I)]
R indices (all data)
R1 / wR2
0.0663 / 0.0877
0.0344 / 0.0756
0.0257 / 0.0472
Ϫ3
˚
Max. peak/hole /e A
0.377 / Ϫ0.415
0.456 / Ϫ0.429
0.464 / Ϫ1.136
Z. Anorg. Allg. Chem. 2006, 295Ϫ300
© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
zaac.wiley-vch.de
299

I. Haiduc, G. Mezei, R. Micu-Semeniuc, F. T. Edelmann, A. Fischer
[(Ph3P)Au{S2P(OPri)C6H4OEt-p}]: A similar procedure with 0.2 g
(Ph3P)AuCl, 0.12 g NH4[S2P(OPri)C6H4OEt-p] gave a viscous oil
which could not be solidified and was discarded.
516, 99; (d) W. E. van Zyl, J. M. Lopez-de-Luzuriaga, A. A.
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Omari, R. J. Staples, J. P. Fackler, Jr., Inorg. Chem. 2003, 42,
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Isaia, V. Lippolis, G. Verani, Inorg. Chim. Acta 1997, 262, 81;
(b) M. C. Aragoni, M. Arca, F. Demartin, F. A. Devillanova,
C. Graiff, F. Isaia, V. Lippolis, A. Tiripicchio, G. Verani, Eur.
J. Inorg. Chem. 2000, 2239; (c) M. C.Aragoni, M. Arca, D. F.
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lanova, J. R. Ferraro, F. Isaia, F. Lelj, V. Lippolis, G. Verani,
Can. J. Chem. 2001, 79, 1483.
Crystallography
The details of crystallographic determinations are given in Table 5.
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Z. Anorg. Allg. Chem. 2006, 295Ϫ300