New gold(I) and silver(I) complexes with organophosphorus ligands with SPNSO skeleton. Crystal and molecular structures of monomeric [Au{(SPPh2)(O2SR)N}(PPh3)] (R = Me, C6H4Me-4) and dimeric [Ag{(SPPh2)(O2SPh)N}(PPh3)]2·2CH2Cl2

Article abstract of DOI:10.1016/j.ica.2009.10.022

The reaction between gold(I) and silver(I) starting materials with anionic organophosphorus ligands of type [(SPPh₂)(O₂SR)N]^- resulted in new group 11 complexes of the type [Au{(SPPh₂)(O₂SR)N}(tht)] (tht = tetrahydrothiophene), [Au{(SPPh₂)(O₂SR)N}(PPh₃)], PPN[Au{(SPPh₂)(O₂SR)N}₂] [PPN = bis(triphenylphosphine)iminium], [Ag{(SPPh₂)(O₂SR)N}] and [Ag{(SPPh₂)(O₂SR)N}(PPh₃)] (R = Me, Ph, C₆H₄CH₃-4). The new derivatives were structurally characterized by ¹H and ³¹P NMR spectroscopy, as well as infrared and mass spectrometry. Single-crystal X-ray diffraction studies revealed monomeric structures for the gold(I) species [Au{(SPPh₂)(O₂SMe)N}(PPh₃)] (4) and [Au{(SPPh₂)(O₂SC₆H₄Me-4)N}(PPh₃)] (6), while a dimeric association was found for the silver(I) compound [Ag{(SPPh₂)(O₂SPh)N}(PPh₃)]₂·2CH₂Cl₂ (14·2CH₂Cl₂). The organophosphorus(V) ligand units have different coordination patterns, i.e. S-monometallic monoconnective in 4, S,O-monometallic biconnective in 6 and S,S,O-bimetallic triconnective in 14, respectively.

Full text of DOI:10.1016/j.ica.2009.10.022

Inorganica Chimica Acta 363 (2010) 346–352
Contents lists available at ScienceDirect
Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
New gold(I) and silver(I) complexes with organophosphorus
ligands with SPNSO skeleton. Crystal and molecular structures
of monomeric [Au{(SPPh2)(O2SR)N}(PPh3)] (R = Me, C6H4Me-4)
and dimeric [Ag{(SPPh2)(O2SPh)N}(PPh3)]2ꢀ2CH2Cl2
b
b
Alpar Pöllnitz a, Anca Silvestru a, , M. Concepción Gimeno , Antonio Laguna
*
a Faculty of Chemistry and Chemical Engineering, ‘‘Babes-Bolyai” University, RO-400028, Cluj-Napoca, Romania
b Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, Universidad de Zaragoza-C.S.I.C., E-50009 Zaragoza, Spain
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 15 August 2009
Received in revised form 21 October 2009
Accepted 28 October 2009
Available online 1 November 2009
The reaction between gold(I) and silver(I) starting materials with anionic organophosphorus ligands of
type [(SPPh2)(O2SR)N]ꢁ resulted in new group 11 complexes of the type [Au{(SPPh2)(O2SR)N}(tht)]
(tht = tetrahydrothiophene), [Au{(SPPh2)(O2SR)N}(PPh3)], PPN[Au{(SPPh2)(O2SR)N}2] [PPN = bis(triphen-
ylphosphine)iminium], [Ag{(SPPh2)(O2SR)N}] and [Ag{(SPPh2)(O2SR)N}(PPh3)] (R = Me, Ph, C6H4CH3-4).
The new derivatives were structurally characterized by 1H and 31P NMR spectroscopy, as well as infrared
and mass spectrometry. Single-crystal X-ray diffraction studies revealed monomeric structures for the
gold(I) species [Au{(SPPh2)(O2SMe)N}(PPh3)] (4) and [Au{(SPPh2)(O2SC6H4Me-4)N}(PPh3)] (6), while a
dimeric association was found for the silver(I) compound [Ag{(SPPh2)(O2SPh)N}(PPh3)]2ꢀ2CH2Cl2
(14ꢀ2CH2Cl2). The organophosphorus(V) ligand units have different coordination patterns, i.e. S-monome-
tallic monoconnective in 4, S,O-monometallic biconnective in 6 and S,S,O-bimetallic triconnective in 14,
respectively.
Keywords:
Gold
Silver
Organophosphorus ligands
Structure elucidation
Ó 2009 Elsevier B.V. All rights reserved.
1. Introduction
complexes with bis(diorganosulfonyl)amido ligands of type A, as
well as of tetraorganodichalcogenoimidodiphosphinato ligands of
Silver(I) [1,2] and gold(I) [3,4] complexes attracted an increased
interest during last years due both to their structural features and
their potential applications. Silver(I) complexes with oxo- or thio
ligands proved to be valuable candidates for catalysis [5], material
science [6,7], or CVD techniques [8]. Gold(I) complexes containing
ligands with N, P or S donor atoms already proved to be valuable
candidates in medicine [9–11], catalysis [12–14] and material sci-
ence [15–17]. Polydentate ligands should offer different coordina-
tion sites, thus dictating different coordination geometries around
the metal centre and the possibility to obtain monomeric or poly-
meric species. Gold(I) diorganodithiophosphinates and -phospho-
nates were intensively investigated in last years related to their
expected metal–metal interactions, thus resulting in dimeric or
polymeric solids with optical properties [18–20]. The dithiolato li-
gands act mostly bimetallic biconnective, bridging the neighboring
gold(I) centres, except the complex [Au{S2P(OMe)(C6H4OEt-
4)}(PPh3)], where the ligand acts monodentate [21]. In the silver(I)
analogues the dithioato ligands act either as bidentate chelating
moieties [22,23] or bridging groups [21]. Group 11 metal
type B, were also described.
Both in silver(I) and gold(I) complexes the ligand of type A is
primarily attached to the metal centre through nitrogen. Gold(I)
complexes [Au{(O2SR)2N}(PPh3)] (R = Me, C6H4Cl-4, C6H4NO2-4
[24], C6H4F-4, C6H4CH3-4 [25]) have monomeric structures with a
linear coordination geometry around the metal center. For the sil-
ver(I) [Ag{(O2SR)2N}2]ꢁ (R = Me, C6H4F-4) anionic species a linear
N–Ag–N core is achieved, but the coordination number of the sil-
ver(I) ion is extended to [2 + 6] by four internal and two external
Agꢀ ꢀ ꢀO secondary interactions [26,27]. The dimeric species
[Ag{(O2SPh)2N}]2(H2O) and [Ag{(O2SC6H4Me-4)2N}]2 [28] are
based on (N,O)-bridging ligands. In the crystal of the water-free
derivative the dimer units are further associated into infinite
strands through two external dative Agꢀ ꢀ ꢀO bonds per silver atom.
Several gold(I) and silver(I) complexes with ligands of type B,
* Corresponding author. Tel.: +40 264 593833; fax: +40 264 590818.
E-mail address: ancas@chem.ubbcluj.ro (A. Silvestru).
0020-1693/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2009.10.022

A. Pöllnitz et al. / Inorganica Chimica Acta 363 (2010) 346–352
347
[(XPR2)(YPR02)N]ꢁ (X, Y = O, S, Se), were investigated as well and
were found to display different coordination patterns [29–31]. A
tetrahedral environment is realized by the S,S-bidentate coordi-
nated protonated ligand in the mononuclear [Ag{(SPPh2)2NH}2]+
cation [32]. The tetranuclear species [Ag{(OPPh2)2N}]4ꢀ2EtOH
contains both (N,O)-bridging ligands and (N,O,O0O0)-trimetallic
tetraconnective ligands [33]. In gold(I) complexes the metal center
retains the expected linear geometry, the imidodiphosphinato
ligands acting in most of the described derivatives as a S-mono-
dentate moiety, i.e. in [Au{(SPPh2)(OPPh2)N}{(SPPh2)(OPPh2)NH}]
[34], [Au{(SPPh2)(OPPh2)N}(Ph2PC6H4NH2)] [35], or [Au{(SPPh2)-
(OPPh2)N}{P-(Ph2P)(OPPh2)NH}] [36]. In the derivative [Au{(SP-
Ph2)2N}(PPh3)] both sulfur atoms are involved in coordination to
the gold(I) center [37].
(MW 657.56): C, 40.18; H, 3.52; N, 2.13; S, 14.63. Found: C,
39.96; H, 3.46; N, 2.14; S, 14.22%. 1H NMR (CDCl3): d 1.96s, br.
(4H, tht), 3.24s, br. (4H, tht), 7.32 m [6H, O2S–C6H5-meta, P(S)–
C6H5-meta], 7.40m [3H, O2S–C6H5-para, P(S)–C6H5-para], 7.91m
[6H, SO2–C6H5-ortho, P(S)–C6H5-ortho], 31P NMR (CDCl3): d 31.2.
ESI+ (m/z, %): 1019 (100) [(tht)2Au2L+Ph]+, 1003 (92),
[(tht)2Au2L+PhꢁO]+, 680 (12) [AuL+Na]+. ESIꢁ (m/z, %): 941 (20)
[AuL2]ꢁ, 595 (100) [AuL+CN]ꢁ, 372 (12) [L]ꢁ. FT-IR (cmꢁ1):
mas(SO2)
1256s; mas(PNS) 1185s; ms(SO2) 1137vs; m(P–S) 570s.
[Au{(SPPh2)(O2SC6H4Me-4)N}(tht)] (3), from K[(SPPh2)(O2SC6-
H4Me-4)N] (0.0425 g, 0.1 mmol) and [AuCl(tht)] (0.032 g,
0.1 mmol). Yield: 0.065 g (97%). M.p. 153 °C (dec). Anal. Calc. for
C23H25AuNO2PS3 (MW 671.59): C, 41.13; H, 3.75; N, 2.08; S,
14.32. Found: C, 40.82; H, 3.57; N, 2.37; S, 14.48%. 1H NMR
(DMSO-d6): d 1.85s, br. (4H, tht), 2.30s (3H, O2S–C6H4CH3), 2.75s,
br. (4H, tht), 7.15d [2H, O2S–C6H4CH3-meta, 3J(HH) 8.0 Hz], 7.42m
[4H, P(S)–C6H5-meta], 7.48m [2H, P(S)–C6H5-para], 7.65d [2H,
Recently we have reported a new class of organophosphorus(V)
ligands of type
C [38,39] and their copper(I) complexes
[CuL(PPh3)2] [39]. Here we report on the synthesis and structural
characterization of some new gold(I) and silver(I) complexes of
type [MLL1], [AuL2]ꢁ or [AgL] (M = Au, Ag, L1 = tht, PPh3, L = ligand
of type C).
3
O2S–C6H4CH3-ortho, J(HH) 8.0 Hz]0 7.83m [4H, P(S)–C6H5-ortho].
31P NMR (DMSO-d6): d 31.0. ESI+ (m/z, %): 1047 (10) [(tht)2Au2L+
Tol]+, 1031 (48), [(tht)2Au2L+TolꢁO]+, 1015 (100) [(tht)2Au2L+
Tolꢁ2O]+, 694 (17) [AuL+Na]+. ESIꢁ (m/z, %): 969 (41) [AuL2]ꢁ,
609 (100) [AuL+CN]ꢁ, 386 (38) [L]ꢁ. FT-IR (cmꢁ1):
m
as(SO2) 1266s,
2. Experimental
1252s; mas(PNS) 1190m; ms(SO2) 1143vs; m(P–S) 568s.
[Au{(SPPh2)(O2SMe)N}(PPh3)] (4), from K[(SPPh2)(O2SMe)N]
(0.035 g, 0.1 mmol) and [AuCl(PPh3)] (0.050 g, 0.1 mmol). Yield:
0.070 g (91%). M.p. 187 °C. Anal. Calc. for C31H28AuNO2P2S2 (MW
769.61): C, 48.38; H, 3.67; N, 1.82; S, 8.33. Found: C, 48.34; H,
3.74; N, 2.08; S, 8.75%. 1H NMR (CDCl3): d 2.94s (3H, O2S–CH3);
7.33m [19H, P(S)–C6H5-meta, P(C6H5)3-ortho + meta + para], 7.49m
[2H, P(S)–C6H5-para], 8.05ddd [4H, P(S)–C6H5-ortho, 3J(HH) 7.1,
4J(HH) 1.2, 3J(PH) 13.9 Hz]. 31P NMR (CDCl3): d 31.6s (PPh3);
37.2s [P(S)–C6H5]. ESI+ (m/z, %): 792 (12) [M+Na]+, 721 (100)
[(PPh3)2Au]+, 508 (22) [AuL+H]+. ESIꢁ (m/z, %): 817 (57) [AuL2]ꢁ,
2.1. General methods
Starting materials, i.e. K[(SPPh2)(O2SR)N] (R = Me, Ph, C6H4Me-
4) [38,39], the gold(I) complexes [AuCl(tht)] [40], [AuCl(PPh3)]
[41], PPN[AuCl2] [42] and silver(I) derivatives [Ag(OTf)(PPh3)]
[43] were prepared according to literature methods or used as pur-
chased (Ag(OTf) – Aldrich). The solvents were dried and freshly
distilled under argon prior to use. Elemental analyses were per-
formed on a Perkin–Elmer 2400 analyser and melting points were
measured on an Electrothermal 9200 apparatus and are not cor-
rected. Infrared spectra were recorded in the range 4000–
400 cmꢁ1 as KBr pellets on a Jasco FTIR-615 machine, while mass
spectra (ESI MS) were performed on an Agilent 6320 Ion Trap
instrument. 1H and 31P NMR spectra were recorded on a BRUKER
Avance DRX 400 instrument. The chemical shifts are reported in
d units (ppm) relative to the residual peak of the deuterated sol-
vent (Ref. CHCl3: 1H 7.26 ppm, DMSO: 1H 2.50 ppm and H3PO4
85%, respectively).
533 (60) [AuL+CN]ꢁ, 310 (100) [L]ꢁ. FT-IR (cmꢁ1):
as(PNS) 1180m; s(SO2) 1140vs, 1121vs;
[Au{(SPPh2)(O2SPh)N}(PPh3)] (5), from K[(SPPh2)(O2SPh)N]
m
as(SO2) 1268s;
m
m
m(P–S) 557s, 538s.
(0.041 g, 0.1 mmol) and [AuCl(PPh3)] (0.050 g, 0.1 mmol). Yield:
0.074 g (89%). M.p. 125 °C (dec.). Anal. Calc. for C36H30AuNO2P2S2
(MW 831.67): C, 51.99; H, 3.63; N, 1.68; S, 7.71. Found: C, 51.83;
H, 3.34; N, 1.51; S, 7.21%. 1H NMR (CDCl3): d 7.14m (3H, O2S–
C6H5-meta + para), 7.24–7.55m [21H, P(S)–C6H5-meta + para,
P(C6H5)3-ortho + meta + para], 7.88d [2H, O2S–C6H5-ortho, 3J(HH)
7.3 Hz], 8.00dd [4H, P(S)–C6H5-ortho, 3J(HH) 8.0, 3J(PH) 13.9 Hz].
31P NMR (CDCl3): d 31.7d [PPh3, 3J(PP) 8.2 Hz], 37.1d [P(S)–C6H5,
3J(PP) 8.4 Hz]. ESI+ (m/z, %): 854 (10) [M+Na]+, 832 (10) [M+H]+,
721 (100) [(PPh3)2Au]+. ESIꢁ (m/z, %): 941 (36) [AuL2]ꢁ, 595 (48)
2.2. Syntheses
2.2.1. Preparation of [Au{(SPPh2)(O2SMe)N}(tht)] (1)
Stoichiometric amounts of K[(SPPh2)(O2SMe)N] (0.035 g,
0.1 mmol) and [AuCl(tht)] (0.032 g, 0.1 mmol) were stirred in
CH2Cl2 (50 mL) for 1 h at room temperature. KCl was removed by
filtration and the solution was concentrated under reduced pres-
sure to approximately 2 mL. The title compound was precipitated
with n-hexane, separated by filtration and dried in vacuum. Yield:
0.05 g (84%). M.p. 130 °C (dec.). Anal. Calc. for C17H21AuNO2PS3
(MW 595.49): C, 34.29; H, 3.55; N, 2.35; S, 16.15. Found: C,
34.42; H, 3.61; N, 2.25; S, 16.34%. 1H NMR (CDCl3): d 1.93s, br.
(4H, tht), 3.01s (3H, O2S–CH3), 3.22s, br. (4H, tht); 7.43m [6H,
P(S)–C6H5-meta + para], 8.01m [4H, P(S)–C6H5-ortho]; 31P NMR
(CDCl3): d 29.9. ESI+ (m/z, %): 895 (62) [(tht)2Au2L+Me]+, 880
(100) [(tht)2Au2L]+, 865 (93) [(tht)2Au2LꢁMe]+, 508 (34) [AuL+H]+.
ESIꢁ (m/z, %): 817 (43) [AuL2]ꢁ, 533 (100) [AuL+CN]ꢁ, 310 (15) [L]ꢁ.
[AuL+CN]ꢁ, 372 (100) [L]ꢁ. FT-IR (cmꢁ1):
1185s; s(SO2) 1138vs; (P–S) 538s.
mas(SO2) 1266s; mas(PNS)
m
m
[Au{(SPPh2)(O2SC6H4Me-4)N}(PPh3)] (6), from K[(SPPh2)(O2S-
C6H4Me-4)N] (0.0425 g, 0.1 mmol) and [AuCl(PPh3)] (0.050 g,
0.1 mmol). Yield: 0.072 g (86%). M.p. 193 °C (dec.). Anal. Calc. for
C37H32AuNO2P2S2 (MW 845.69): C, 52.55; H, 3.81; N, 1.65; S,
7.58. Found: C, 52.35; H, 3.84; N, 1.73; S, 7.65%. 1H NMR (CDCl3):
d 2.17s (3H, O2S–C6H4CH3), 6.88d [2H, O2S–C6H4CH3-meta, 3J(HH)
7.8 Hz], 7.21–7.51m [21H, P(C6H5)3-ortho + meta + para, P(S)–
C6H5-meta + para], 7.76d [2H, O2S–C6H4CH3-ortho, 3J(HH) 7.9 Hz],
7.98dd [4H, P(S)–C6H5-ortho, 3J(HH) 7.5, 3J(PH) 13.8 Hz]. 31P NMR
(CDCl3): d 31.4s, br. (PPh3), 37.1s [P(S)–C6H5]. ESI+ (m/z, %): 868
(37) [M+Na]+, 721 (100) [(PPh3)2Au]+. ESIꢁ (m/z, %): 969 (28)
[AuL2]ꢁ, 609 (20) [AuL+CN]ꢁ, 386 (100) [L]ꢁ. FT-IR (cmꢁ1):
m
as(SO2)
FT-IR (cmꢁ1):
1109vs; (P–S) 568s.
Compounds 2–6 were prepared similarly:
m
as(SO2) 1241s;
m
as(PNS) 1180s;
ms(SO2) 1142vs,
1250vs;
mas(PNS) 1181m; ms(SO2) 1155vs, 1131vs; m(P–S) 566s.
m
2.2.2. Preparation of PPN[Au{(SPPh2)(O2SMe)N}2] (7)
[Au{(SPPh2)(O2SPh)N}(tht)] (2), from K[(SPPh2)(O2SPh)N]
(0.041 g, 0.1 mmol) and [AuCl(tht)] (0.032 g, 0.1 mmol). Yield:
0.06 g (92%). M.p. 65 °C (dec). Anal. Calc. for C22H23AuNO2PS3
Stoichiometric amounts of K[(SPPh2)(O2SMe)N] (0.070 g,
0.2 mmol) and PPN[AuCl2] (0.080 g, 0.1 mmol) were stirred in
CH2Cl2 (50 mL) for 1 h at room temperature. KCl was removed by

348
A. Pöllnitz et al. / Inorganica Chimica Acta 363 (2010) 346–352
filtration and the solution was concentrated under reduced pres-
sure to approximately 2 mL. The title compound was precipitated
with n-hexane, separated by filtration and dried in vacuum. Yield:
0.126 g (93%). M.p. 88–90 °C. Anal. Calc. for C62H56AuN3O4P4S4
(MW 1356.27): C, 54.91; H, 4.16; N, 3.10; S, 9.46. Found: C,
54.79; H, 4.60; N, 3.48; S, 9.06. 1H NMR (CDCl3): d 2.93s (6H,
O2S–CH3); 7.28m [8H, P(S)–C6H5-meta], 7.34m [4H, P(S)–C6H5-
para]; 7.45m [24H, N(PPh3)2-ortho + meta], 7.65m [6H, N(PPh3)2-
para], 7.97ddd [8H, P(S)–C6H5-ortho, 3J(HH) 7.0, 4J(HH) 1.4, 3J(PH)
13.7 Hz]. 31P NMR (CDCl3): d 21.2s [N(PPh3)2]; 32.6s [P(S)–C6H5].
ESI+ (m/z, %): 538 (100) [PPN]+. ESIꢁ (m/z, %): 817 (100) [AuL2]ꢁ,
3J(HH) 7.5 Hz], 7.75dd [4H, P(S)–C6H5-ortho, 3J(HH) 7.3, 3J(PH)
14.1 Hz). 31P NMR (CDCl3):
d 37.3. ESI+ (m/z, %): 855 (80)
[Ag2L2ꢁ2SO2+Na]+, 832 (100) [Ag2L2ꢁ2SO2]+. ESIꢁ (m/z, %): 853
(100) [AgL2]ꢁ, 372 (10) [L]ꢁ. FT-IR (cmꢁ1):
mas(SO2) 1253vs;
mas(PNS) 1178s;
ms(SO2) 1134s, 1079m, 1051s; m(P@S) 656s; m(P–
S) 591s.
[Ag{(SPPh2)(O2SC6H4Me-4)N}] (12), from K[(SPPh2)(O2SC6H4-
Me-4)N] (0.0425 g, 0.1 mmol) and Ag(OTf) (0.0256 g, 0.1 mmol).
Yield: 0.038 g (77%). M.p. 170 °C (dec.). Anal. Calc. for C19H17Ag-
NO2PS2 (MW 494.32): C, 46.17; H, 3.46; N, 2.83; S, 12.97. Found:
C, 46.49; H, 3.35; N, 2.76; S, 13.19%. 1H NMR (CDCl3): d 2.28s
(3H, O2S–C6H4CH3), 6.95d [2H, O2S–C6H4CH3-meta, 3J(HH)
7.7 Hz]; 7.25m [4H, P(S)–C6H5-meta]; 7.36t [2H, P(S)–C6H5-para,
3J(HH) 7.1 Hz); 7.54d [2H, O2S–C6H4CH3-ortho, 3J(HH) 7.8 Hz],
7.76dd [4H, P(S)–C6H5-ortho, 3J(HH) 7.8, 3J(PH) 13.8 Hz]. 31P NMR
(CDCl3): d 37.5. ESI+ (m/z, %): 883 (100) [Ag2L2ꢁ2SO2+Na]+, 860
(32) [Ag2L2ꢁ2SO2]+. ESIꢁ (m/z, %): 881 (100) [AgL2]ꢁ, 386 (28)
310 (12) [L]ꢁ. FT-IR (cmꢁ1):
s(SO2) 1117vs; (P–S) 565s, 548s.
Compounds 8 and 9 were prepared similarly:
PPN[Au{(SPPh2)(O2SPh)N}2] (8), from K[(SPPh2)(O2SPh)N]
mas(SO2) 1264vs; mas(PNS) 1180m;
m
m
(0.082 g, 0.2 mmol) and PPN[AuCl2] (0.080 g, 0.1 mmol). Yield:
0.133 g (94%). M.p. 94–95 °C. Anal. Calc. for C72H60AuN3O4P4S4
(MW 1480.39): C, 58.42; H, 4.09; N, 2.84; S, 8.66. Found: C,
58.52, H, 4.11; N, 3.02; S, 8.92%. 1H NMR (CDCl3): d 7.12–7.31m
[18H, P(S)–C6H5-meta + para, O2S–C6H5-meta + para], 7.44m [24H,
N(PPh3)2-ortho + meta], 7.63dt [6H, N(PPh3)2-para, 3J(HH) 7.0,
4J(HH) 1.9 Hz], 7.82dd [8H, P(S)–C6H5-ortho, 3J(HH) 7.6, 3J(PH)
10.8 Hz], 7.84d [4H, O2S–C6H5-ortho, 3J(HH) 7.6 Hz]. 31P NMR
(CDCl3): d 21.2s [N(PPh3)2], 33.4s [P(S)–C6H5]. ESI+ (m/z, %): 538
(100) [PPN]+. ESIꢁ (m/z, %): 941 (100) [AuL2]ꢁ, 372 (10) [L]ꢁ. FT-
[L]ꢁ. FT-IR (cmꢁ1):
1132s, 1079m, 1037s;
m
m
as(SO2) 1252vs;
mas(PNS) 1175s; ms(SO2)
(P@S) 655s; (P–S) 590s.
m
2.2.4. Preparation of [Ag{(SPPh2)(O2SMe)N}(PPh3)] (13)
Stoichiometric amounts of K[(SPPh2)(O2SMe)N] (0.035 g,
0.1 mmol) and [Ag(OTf)(PPh3)] (0.052 g, 0.1 mmol) were stirred
in acetone (50 mL) for 1 h at room temperature, in a flask covered
with tin foil. KOTf was removed by filtration and the solution was
concentrated under reduced pressure to approximately 2 mL. The
title compound was precipitated with n-hexane, separated by fil-
tration and dried in vacuum. Yield: 0.059 g (87%). M.p. 211 °C
(dec.). Anal. Calc. for C31H28AgNO2P2S2 (MW 680.51): C, 54.71; H,
4.15; N, 2.06; S, 9.42. Found: C, 54.43; H, 3.98; N, 2.14; S, 8.84%.
1H NMR (CDCl3): d 2.64s (3H, O2S–CH3), 7.29m [21H, P(C6H5)3-
ortho + meta + para, P(S)–C6H5-meta + para], 7.91dd [4H, P(S)–
C6H5-ortho, 3J(HH) 7.3, 3J(PH) 13.5 Hz]. 31P NMR (CDCl3): d 6.6s
(PPh3); 37.3s [P(S)–C6H5]. ESI+ (m/z, %): 631 (100) [(PPh3)2Ag]+.
ESIꢁ (m/z, %): 1146 (5), [Ag2L3]ꢁ, 729 (68) [AgL2]ꢁ, 310 (100)
IR (cmꢁ1):
1115vs; (P–S) 534m.
mas(SO2) 1266vs; mas(PNS) 1180m; ms(SO2) 1140vs,
m
PPN[Au{(SPPh2)(O2SC6H4Me-4)N}2] (9), from K[(SPPh2)(O2S-
C6H4Me-4)N] (0.0852 g, 0.2 mmol) and PPN[AuCl2] (0.080 g,
0.1 mmol). Yield: 0.128 g (89%). M.p. 84–85 °C. Anal. Calc. for
C74H64AuN3O4P4S4 (MW 1507.24): C, 58.92; H, 4.28; N, 2.79; S,
8.50. Found: C, 58.88; H, 4.20; N, 2.71; S, 8.41%. 1H NMR (CDCl3):
2.26s (6H, O2S–C6H4CH3); 6.96d [4H, O2S–C6H4CH3-meta, 3J(HH)
7.9 Hz], 7.15m [8H, P(S)–C6H5-meta], 7.25t [4H, P(S)–C6H5-para,
3J(HH) 7.2 Hz], 7.44m [24H, N(PPh3)2-ortho + meta], 7.62m (6H,
N(PPh3)2-para], 7.71d [2H, O2S–C6H4CH3-ortho, 3J(HH) 8.0 Hz],
7.81dd [4H, P(S)–C6H5-ortho, 3J(HH) 7.4, 3J(PH) 13.7 Hz]. 31P NMR
(CDCl3): d 21.2s [N(PPh3)2], 33.0s [P(S)–C6H5]. ESI+ (m/z, %): 538
(100) [PPN]+. ESIꢁ (m/z, %): 969 (100) [AuL2]ꢁ, 386 (10) [L]ꢁ. FT-
[L]ꢁ. FT-IR (cmꢁ1):
1156m; (P–S) 570s.
Compounds 14 and 15 were prepared similarly:
mas(SO2) 1243s; mas(PNS) 1198s; ms(SO2)
m
IR (cmꢁ1):
1114vs; (P–S) 569s.
m
as(SO2) 1265s;
mas(PNS) 1181m;
m
s(SO2) 1138vs,
[Ag{(SPPh2)(O2SPh)N}(PPh3)]2 (14), from K[(SPPh2)(O2SPh)N]
(0.041 g, 0.1 mmol) and [Ag(OTf)(PPh3)] (0.052 g, 0.1 mmol). Yield:
0.063 g (85%). M.p. 170–171 °C. Anal. Calc. for C36H30AgNO2P2S2
(MW 742.58): C, 58.23; H, 4.07; N, 1.89; S, 8.64. Found: C, 58.09;
H, 3.99; N, 1.81; S, 9.19%. 1H NMR (CDCl3): d 7.08t [2H, O2S–
C6H5-meta, 3J(HH) 7.1 Hz], 7.21m [5H, P(S)–C6H5-meta, O2S–C6H5-
para]; 7.32m [17H, P(C6H5)3-ortho + meta + para, P(S)–C6H5-para],
7.67d [2H, O2S–C6H5-ortho, 3J(HH) 7.3 Hz], 7.84dd [4H, P(S)–
C6H5-ortho, 3J(HH) 7.4, 3J(PH) 13.8 Hz), 31P NMR (CDCl3): d 6.6s
(PPh3); 38.7s [P(S)–C6H5]. ESI+ (m/z, %): 631 (100) [(PPh3)2Ag]+.
ESIꢁ (m/z, %): 1335 (10), [Ag2L3]ꢁ, 853 (100) [AgL2]ꢁ, 372 (32)
m
2.2.3. Preparation of [Ag{(SPPh2)(O2SMe)N}] (10)
Stoichiometric amounts of K[(SPPh2)(O2SMe)N] (0.035 g,
0.1 mmol) and Ag(OTf) (0.0256 g, 0.1 mmol) were stirred in ace-
tone (50 mL) for 1 h at room temperature, in a flask covered with
tin foil. KOTf was removed by filtration and the solution was con-
centrated under reduced pressure to approximately 2 mL. The title
compound was precipitated with n-hexane, separated by filtration
and dried in vacuum. Yield: 0.037 g (88%). M.p. 177 °C (dec.). Anal.
Calc. for C13H13AgNO2PS2 (MW 418.22): C, 37.33; H, 3.13; N, 3.34;
S, 15.33. Found: C, 37.62; H, 3.23; N, 3.25; S, 15.02%. 1H NMR
(CDCl3): d 2.63s (3H, O2S–CH3); 7.37m [4H, P(S)–C6H5-meta],
7.43m [2H, P(S)–C6H5-para], 7.88dd [4H, P(S)–C6H5-ortho, 3J(HH)
7.2, 3J(PH) 13.9 Hz]. 31P NMR (CDCl3): d 36.8. ESI+ (m/z, %): 626
(100) [Ag2L+MeSO2+Na]+ ESIꢁ (m/z, %): 729 (100) [AgL2]ꢁ, 310
[L]ꢁ. FT-IR (cmꢁ1):
1132vs; (P–S) 576s.
mas(SO2) 1254vs; mas(PNS) 1162m; ms(SO2)
m
[Ag{(SPPh2)(O2SC6H4Me-4)N}(PPh3)] (15), from K[(SPPh2)(O2S-
C6H4Me-4)N] (0.0425 g, 0.1 mmol) and [Ag(OTf)(PPh3)] (0.052 g,
0.1 mmol). Yield: 0.071 g (96%). M.p. 162–163 °C. Anal. Calc. for
C37H32AgNO2P2S2 (MW 756.60): C, 58.73; H, 4.26; N, 1.85; S,
8.48. Found: C, 58.50; H, 4.04; N, 2.02; S, 7.83%. 1H NMR (CDCl3):
d 2.22s (3H, O2S–C6H4CH3); 6.82d [2H, O2S–C6H4CH3-meta, 3J(HH)
8.0 Hz], 7.17dt [4H, P(S)–C6H5-meta, 3J(HH) 7.4, 4J(PH) 3.4 Hz],
7.27m [14H, P(C6H5)3-ortho + meta, P(S)–C6H5-para], 7.37t [3H,
P(C6H5)3-para, 3J(HH) 7.6 Hz], 7.53d [2H, O2S–C6H4CH3-ortho,
3J(HH) 8.1 Hz], 7.76dd [4H, P(S)–C6H5-ortho, 3J(HH) 7.2, 3J(PH)
13.7 Hz], 31P NMR (CDCl3): d 7.7s (PPh3), 37.7s [P(S)-C6H5]. ESI+
(m/z, %): 631 (100) [(PPh3)2Ag]+. ESIꢁ (m/z, %): 1374 (5) [Ag2L3]ꢁ,
(82) [L]ꢁ. FT-IR (cmꢁ1):
1165vs; s(SO2) 1111s, 1095s, 1040s;
Compounds 11 and 12 were prepared similarly:
m
as(SO2) 1266vs, 1230s, 1216s;
mas(PNS)
m
m
(P@S) 645s; (P–S) 597s.
m
[Ag{(SPPh2)(O2SPh)N}] (11), from K[(SPPh2)(O2SPh)N] (0.041 g,
0.1 mmol) and Ag(OTf) (0.0256 g, 0.1 mmol). Yield: 0.042 g (88%).
M.p. 128–130 °C. Anal. Calc. for C18H15AgNO2PS2 (MW 480.29): C,
45.02; H, 3.15; N, 2.92; S, 13.35. Found: C, 44.89; H, 2.98; N,
2.80; S, 12.93%. 1H NMR (CDCl3): d 7.16t [2H, O2S–C6H5-meta,
3J(HH) 7.8 Hz], 7.27m [5H, P(S)–C6H5-meta, SO2–C6H5-para], 7.38t
[2H, P(S)–C6H5-para, 3J(HH) 7.4 Hz], 7.63d [2H, O2S–C6H5-ortho,
881 (100) [AgL2]ꢁ, 386 (23) [L]ꢁ. FT-IR (cmꢁ1):
as(PNS) 1183m; s(SO2) 1153vs, 1126vs; (P–S) 592vs.
mas(SO2) 1262vs;
m
m
m

A. Pöllnitz et al. / Inorganica Chimica Acta 363 (2010) 346–352
349
Table 1
Crystallographic data for [Au{(SPPh2)(O2SMe)N}(PPh3)] (4), [Au{(SPPh2)(O2SC6H4Me-4)N}(PPh3)] (6) and [Ag{(SPPh2)(O2SPh)N}(PPh3)]2ꢀ2CH2Cl2 (14ꢀ2CH2Cl2).
Compound
4
6
14ꢀ2CH2Cl2
Empirical formula
Formula weight
Crystal size (mm)
Temperature (K)
Wavelength (Å)
Crystal system
Space group
a (Å)
C31H28AuNO2P2S2
769.57
C37H32AuNO2P2S2
845.66
C74H64Ag2Cl4N2O4P4S4
1654.97
0.26 ꢃ 0.15 ꢃ 0.15
0.32 ꢃ 0.23 ꢃ 0.18
0.23 ꢃ 0.22 ꢃ 0.19
297(2)
297(2)
297(2)
0.71073
Monoclinic
C2/c
27.499(2)
8.9413(7)
26.836(2)
90.00
116.591(1)
90.00
0.71073
Trigonal
P3(2)
10.4687(4)
10.4687(4)
27.184(2)
90.00
90.00
120.00
0.71073
Triclinic
ꢀ
P1
10.7507(13)
13.6911(17)
13.8693(17)
103.806(2)
91.200(2)
112.646(2)
1815.0(4)
1
b (Å)
c (Å)
a
(°)
b (°)
c
(°)
V (Å3)
5900.3(8)
8
1.733
2580.1(2)
3
1.633
Z
Dcalc (mg mꢁ3
)
1.514
0.940
l
(mmꢁ1
)
5.267
4.525
F (0 0 0)
3024
1254
840
h Range for data collections (°)
Maximum and minimum transmission
Reflections collected
1.66–26.37
0.454 and 0.403
23090
2.25–25.02
0.443 and 0.298
18696
1.94–25.00
0.8416 and 0.8128
17655
Independent reflections
Refinement method
6023 [Rint = 0.0412]
Full-matrix least-squares on F2
6023/0/353
1.074
6006 [Rint = 0.0401]
6379 [Rint = 0.0417]
Data/restraints/parameters
6006/1/407
0.989
6379/0/424
1.095
Goodness-of-fit on F2
Final R indices [I > 2
R indices (all data)
r(I)]
R1 = 0.0330
wR2 = 0.0670
R1 = 0.0393
wR2 = 0.0693
1.061, ꢁ0.453
R1 = 0.0312
wR2 = 0.0641
R1 = 0.0330
wR2 = 0.0648
0.831, ꢁ1.063
R1 = 0.0522
wR2 = 0.1050
R1 = 0.0670
wR2 = 0.1103
0.557, ꢁ0.315
Final
K )
-map (e Åꢁ3
½AgOTfꢂ þ K½ðSPPh2ÞðO2SRÞNꢂ
! ½AgfðSPPh2ÞðO2SRÞNgꢂ þ KOTf
R ¼ Me ð10Þ; Ph ð11Þ; C6H4Me-4 ð12Þ
2.3. Crystal structure determination of compounds 4, 6 and
14ꢀ2CH2Cl2
ð3Þ
ð4Þ
Colorless crystals of compounds 4, 6 and 14ꢀ2CH2Cl2 were
grown by slow diffusion in CH2Cl2/n-hexane (1/5, v/v) systems.
The crystals were attached with epoxy glue on cryoloops. Data
collection and processing was carried on a Bruker SMART APEX
system (Babes-Bolyai University, Cluj-Napoca) using graphite-
n½AgOTfðPPh3Þꢂ þ nK½ðSPPh2ÞðO2SRÞNꢂ
! ½AgfðSPPh2ÞðO2SRÞNgðPPh3Þꢂn þ nKOTf
n ¼ 1; R ¼ Me ð13Þ; C6H4Me-4 ð15Þ
n ¼ 1; R ¼ Ph ð14Þ
monochromated Mo Ka radiation (k = 0.71073 Å). Details of the
crystal structure determination and refinement for compounds 4,
6 and 14ꢀ2CH2Cl2 are given in Table 1.
Scan type
x and U. Absorption corrections: multi-scan [44]. The
All compounds described in this paper are colorless crystalline
solids. NMR data and elemental analysis are consistent with the
desired compounds.
structures were refined with anisotropic thermal parameters. The
hydrogen atoms were refined with a riding model and a mutual
isotropic thermal parameter. For structure solving and refinement
the software package SHELX-97 was used [45]. The drawings were
created with the DIAMOND program [46].
For the phenyl groups attached to phosphorus the 1H NMR spec-
tra showed resonances with the expected pattern due to the pro-
ton–proton and phosphorus–proton couplings, respectively. The
31P NMR spectra of the complexes exhibit one or two resonances,
corresponding to the P(S)Ph2 moiety and the PPh3 or the PPN
groups, respectively, consistent with the presence of only one spe-
cies in solution. Mass spectra (ESI) suggest a dimeric structure for
the gold derivatives 1–3 and the silver compounds 10–15. In case
of these compounds in the ESI+ mass spectra were observed peaks
corresponding to fragments with a greater mass than that corre-
sponding to the monomers, i.e. the [(tht)2Au2L]+ ion or ions derived
from this (m/z = 879 in 1, 1019 in 2 and 1031 in 3), as well as ions
derived from the Ag2L or Ag2L2 moiety (m/z 626 in 10, 855 in 11,
and 883 in 12). For derivatives 13–15 the ESIꢁ mass spectra present
characteristic ions for the formula [Ag2L3]ꢁ, in accordance with the
dimeric structure of 14ꢀ2CH2Cl2 determined by single-crystal X-ray
diffraction. However, for all compounds in ESIꢁ spectra appear the
[ML2]ꢁ (M = Au or Ag) ion accompanied by the [L]ꢁ ion.
3. Results and discussion
3.1. Preparation and solution NMR characterization
The gold(I) and silver(I) complexes were obtained by salt
metathesis reactions between the potassium salt of the appropri-
ate organophosphorus acid and the corresponding gold- or silver-
containing starting material, according to Eqs. (1)–(4)
½AuCILꢂ þ K½ðSPPh2ÞðO2SRÞNꢂ
! ½AufðSPPh2ÞðO2SRÞNgLꢂ þ KCl
L ¼ tht; R ¼ Me ð1Þ; Ph ð2Þ; C6H4Me-4 ð3Þ
L ¼ PPh3; R ¼ Me ð4Þ; Ph ð5Þ; C6H4Me-4 ð6Þ
ð1Þ
ð2Þ
For all compounds the IR spectra recorded as KBr discs show no
PPN½AuCL2ꢂ þ 2K½ðSPPh2ÞðO2SRÞNꢂ
strong absorption around 900 cmꢁ1
[mas[PN(H)S)], typical for the
! PPN½AufðSPPh2ÞðO2SRÞNg2ꢂ þ 2KCl
R ¼ Me ð7Þ; Ph ð8Þ; C6H4Me-4 ð9Þ
free acids, thus indicating that the ligands moieties are present in
the deprotonated form. Medium to very strong bands were

350
A. Pöllnitz et al. / Inorganica Chimica Acta 363 (2010) 346–352
Fig. 1. ORTEP plot of [Au{(SPPh2)(O2SMe)N}(PPh3)] (4). The atoms are drawn with
30% probability ellipsoids.
assigned to
m
as(SO2) (1270–1200 cmꢁ1),
m
as(PNS) (1200–1160
cmꢁ1), s(SO2) (1160–1040 cmꢁ1) and
m
m
(P–S) (600–530 cmꢁ1
)
stretching vibrations, consistent with covalent metal–sulfur bonds
[47–49]. However, the IR spectra of compounds 10–12 contain an
additional strong band in the region 660–640 cmꢁ1, typical for a
P@S stretching vibration, thus suggesting that ligands attached pri-
marily to silver through oxygen are also present.
Fig. 2. ORTEP plot of [Au{(SPPh2)(O2SC6H4Me-4)N}(PPh3)] (6). The atoms are drawn
with 30% probability ellipsoids. Hydrogen atoms are omitted for clarity.
involved in interactions with the gold center, the Au–O distances
being much longer than the sum of the van der Waals radii for gold
3.2. Crystal and molecular structure of 4 and 6
and oxygen [Auꢀ ꢀ ꢀO 5.697(3) and 4.551(3) Å versus
RrvdW(Au, O)
3.10 Å] [51].
The ORTEP-like representations for compounds 4 and 6 are de-
picted in Figs. 1 and 2, while relevant bond distances and angles
are given in Table 2.
In 6 the organophosphorus ligand is also covalently attached to
the metal center through sulfur [Au(1)–S(1) 2.3024(17) Å], but, in
contrast to the molecule of 4, the SPNSO2 skeleton is twisted,
probably due to crystal packing, to bring the O2SR moiety closer
to the metal centre. A weak secondary Au(1)ꢀ ꢀ ꢀO(2) intramolecular
interaction [2.986(5) Å] and thus an S,O-monometallic biconnec-
tive coordination pattern might be considered in 6, similarly
to the situation found in the copper(I) complexes [Cu{(SPPh2)-
(O2SR)N}(PPh3)2] (R = Me, C6H4Me-4) [39]. The result is a distorted
T-shaped coordination geometry around the gold center
The gold(I) complexes 4 and 6 have mononuclear structures,
with no intermolecular Auꢀ ꢀ ꢀAu contacts shorter than 3.3 Å [50].
The organophosphorus(V) ligand behaves as
a monometallic
monoconnective moiety in 4, being coordinated to the gold centre
only through the sulfur atom attached to phosphorus [Au(1)–S(1)
2.3136(10) Å versus
Rrcov(Au, S) 2.38 Å] [51], thus resulting in a
distorted linear coordination geometry around gold [P(1)–Au(1)–
S(1) 175.71(4)°]. The oxygen atoms in the O2SR moiety are not
Table 2
Important interatomic distances (Å) and angles (°) for compounds 4, 6 and 14ꢀ2CH2Cl2.
a
4
6
14ꢀ2CH2Cl2
Au(1)–P(1)
Au(1)–S(1)
2.2545(10)
2.3136(10)
Au(1)–P(1)
Au(1)–S(1)
Au(1)ꢀ ꢀ ꢀO(2)
2.2510(16)
2.3024(17)
2.986(5)
Ag(1)–P(2)
Ag(1)–O(1)
Ag(1)–S(1)
Ag(1)–S(1a)
N(1)–S(2)
N(1)–P(1)
P(1)–S(1)
2.4025(11)
2.491(3)
2.7008(11)
2.5384(11)
1.560(3)
1.598(3)
2.0025(14)
1.450(3)
N(1)–S(2)
N(1)–P(2)
P(2)–S(1)
O(1)–S(2)
O(2)–S(2)
1.577(4)
1.601(3)
2.0478(14)
1.432(3)
1.438(3)
N(1)–S(2)
N(1)–P(2)
P(2)–S(1)
O(1)–S(2)
O(2)–S(2)
1.569(5)
1.579(5)
2.038(2)
1.432(4)
1.439(4)
O(1)–S(2)
O(2)–S(2)
1.427(3)
P(1)–Au(1)–S(1)
P(2)–S(1)–Au(1)
175.71(4)
98.26(5)
P(1)–Au(1)–S(1)
P(2)–S(1)–Au(1)
176.79(6)
99.11(8)
P(2)–Ag(1)–O(1)
P(2)–Ag(1)–S(1)
O(1)–Ag(1)–S(1)
P(2)–Ag(1)–S(1a)
O(1)–Ag(1)–S(1a)
S(1)–Ag(1)–S(1a)
Ag(1)–S(1)–Ag(1a)
N(1)–P(1)–S(1)
O(1)–S(2)–O(2)
S(2)–N(1)–P(1)
102.54(7)
122.05(4)
91.17(6)
141.70(4)
98.85(7)
88.56(3)
91.44(3)
118.29(13)
115.86(18)
129.0(2)
N(1)–P(2)–S(1)
O(1)–S(2)–O(2)
S(2)–N(1)–P(2)
119.34(14)
115.1(2)
126.2(2)
N(1)–P(2)–S(1)
O(1)–S(2)–O(2)
S(2)–N(1)–P(2)
118.7(2)
115.2(3)
129.1(3)
a
Symmetry equivalent positions (1ꢁx, 1ꢁy, ꢁz) are given by ‘‘a”.

A. Pöllnitz et al. / Inorganica Chimica Acta 363 (2010) 346–352
351
[P(1)–Au(1)–S(1) 176.79(6)°, P(1)–Au(1)ꢀ ꢀ ꢀO(2) 89.38(8)°, S(1)–
Au(1)ꢀ ꢀ ꢀO(2) 93.82(8)°]. In addition, the same O(2) atom is
involved in
weak intramolecular C(2)–H(2)ꢀ ꢀ ꢀO(2) contact
[2.541(4) Å versus rcov(O, H) 2.60 Å] [51]. The second oxygen
a
R
atom is placed far away from the coordination sphere of gold
[Au(1)ꢀ ꢀ ꢀO(1) 5.220(5) Å] and is not involved in any interaction.
The weakness of the intramolecular Auꢀ ꢀ ꢀO interaction in 6 is con-
sistent with the fact that no significant difference can be observed
between the two sulfur–oxygen distances of the ligand unit, a
behavior also noted for the complex 4 in which the ligand acts as
monodentate moiety.
In the crystal there should be noted intramolecular C–Hꢀ ꢀ ꢀ
p
contacts [3.15 Å in 4 and 3.06 Å in 6] [52], between the hydrogen
of a C–H bond from a phenyl ring of the PPh3 ligand and one of
the aromatic ring from the Ph2PS moiety of the anionic ligand.
The six membered AuSPNSO ring in 6 has a twisted boat confor-
mation, with P(2) and O(2) in apices, at 0.964 and 0.35 Å, respec-
tively, from the Au(1)S(1)N(1)S(2) best plane. The P(2)–S(1) bond
distances [2.0478(14) Å in 4 and 2.038(2) Å in 6] are longer, while
the N(1)–P(2) [1.601(3) Å in 4 and 1.579(5) Å in 6] and N(1)–S(2)
[1.577(4) Å in 4 and 1.569(5) Å in 6] bond distances are shorter
than in the corresponding protonated ligands [cf. P–S, N–P
and N–S in (SPPh2)(O2SMe)NH: 1.9284(7)/1.708(2)/1.634(2) Å;
(SPPh2)(O2SC6H4Me-4)NH: 1.9326(8)/1.703(1)/1.641(1) Å] [38].
Their magnitude is intermediate between double and single
phosphorus–sulfur, phosphorus–nitrogen or sulfur–nitrogen
bonds, respectively. Surprisingly, the sulfur–oxygen bonds in the
N–SO2R moiety of the complexes [S(2)–O(1)/S(2)–O(2) 1.432(3)/
1.438(3) Å in 4 and 1.432(4)/1.439(4) Å in 6] are of the same
magnitude to the double S@O bonds observed in the protonated
ligands [i.e. (SPPh2)(O2SMe)NH: 1.427(1)/1.428(1) Å; (SPPh2)(O2-
SC6H4Me-4)NH: 1.429(1)/1.446(1) Å] [38]. The lengths of the
Au(1)–P(1) bond [2.2545(10) Å in 4 and 2.2510(16) Å in 6] are of
the same magnitude as in the gold precursor [AuCl(PPh3)] [P–Au
2.235(3) Å] [53] and other complexes containing the Au(PR3) frag-
ment [20,21,24,54,55].
Fig. 3. ORTEP plot of the dimeric unit of [Ag{(SPPh2)(O2SPh)N}(PPh3)]2
(14ꢀ2CH2Cl2). The atoms are drawn with 30% probability ellipsoids. Hydrogen
atoms and CH2Cl2 are omitted for clarity.
S(1)/P(2) basal plane. The bond angles at the metal centre range
between 88.56(3) and 141.70(4)° (see Table 2). The whole tricyclic
system in 14 is similar to the central part of the tetranuclear deriv-
ative [Ag{(OPPh2)2N}]4ꢀ2EtOH, which contain a central planar
Ag2O2 ring and tetrahedral AgO4 cores [33].
The P(1)–S(1) [2.0025(14) Å], N(1)–P(1) [1.598(3) Å] and N(1)–
S(2) [1.560(3) Å] bond distances in 14 are similar to those found
in the gold(I) derivatives described above (see Table 2) and for
the [Cu{(SPPh2)(O2SR)N}(PPh3)2] derivatives [P–S 1.9886(14), P–N
1.602(3) for R = Me; P–S 1.995(2) Å, P–N 1.605(6) for
R = C6H4Me-4] [39], which contain S,O-monometallic biconnective
ligand moieties, indicating an intermediate magnitude between
double and single bonds. Although only O(1) atom is involved in
a strong interaction with a silver atom in 14, this is only slightly re-
flected in the lengths of the two sulfur–oxygen bonds of the N–
SO2Ph moiety [O(1)–S(2)/O(2)–S(2) 1.450(3)/1.427(3) Å], indicat-
ing a considerable double bond character for the O(1)–S(2) bond
[cf. (SPPh2)(O2SPh)NH: O(1)–S(2)/O(2)–S(2) 1.422(2)/1.429(2) Å].
All attempts to obtain single crystals suitable for X-ray diffrac-
tion studies for the related compounds 13 and 15 or for those of
the type [Ag{(SPPh2)(O2SR)N}] [R = Me (10), Ph (11), C6H4Me-4
(12)] failed. Complexes 13 and 15 are very likely to exhibit in solid
state a dimeric structure similar to that established for compound
14. Taking into account the analogy between ligands of type A, B
and C, it is plausible to assume that solid state clusters or poly-
meric associations based on silver–oxygen, silver–sulfur and/or
even silver–nitrogen interactions are expected for compounds
10–12, as found for example in the related [Ag{(O2SR)2N}]n
(R = Me [57], C6H4I-4 [58]), [Ag{(OPPh2)2N}]4ꢀ2EtOH [33], [Ag{(X-
PiPr2)2N}]3 (X = Se [59], S [60]), X [Ag{(SePPh2)2N}]4 [31].
Attempts to obtain single-crystals suitable for X-ray diffraction
studies for compounds of the type [Au{(SPPh2)(O2SR)N}(tht)]
[R = Me (1), Ph (2), C6H4Me-4 (3)], and PPN[Au{(SPPh2)(O2SR)N}2]
[R = Me (7), Ph (8), C6H4Me-4 (9)] failed. Taking into account the
ESI MS data for derivatives 1–3, as well as the existence of Auꢀ ꢀ ꢀAu
interactions in complexes of type [AuX(tht)] (X = Cl, Br) [56], a di-
meric structure could be assumed for these derivatives, while for
compounds 7–9 monomeric structures with a linear S–Au–S core
can be assigned.
3.3. Crystal and molecular structure of 14ꢀ2CH2Cl2
The ORTEP-like representation for compound 14ꢀ2CH2Cl2 is de-
picted in Fig. 3, while relevant bond distances and angles are given
in Table 2.
The crystal of the complex 14 consists of centrosymmetric dinu-
clear units in which the organophosphorus(V) ligands act as S,O-
bridges between two silver(I) atoms [Ag(1a)–S(1) 2.5384(11) Å,
Ag(1)–O(1) 2.491(3) Å; cf.
R
rcov(Ag, S) 2.38 Å/RrvdW(Ag, S) 3.55 Å,
and rcov(Ag, O) 2.00 Å/
R
RrvdW(Ag, O) 3.10 Å] [51], resulting in a
twelve-membered cycle. In addition, transannular Agꢀ ꢀ ꢀS interac-
tions are also present [Ag(1)–S(1) 2.7008(11) Å], the overall coordi-
nation pattern of the ligand being S,S,O-bimetallic triconnective.
The resulting tricyclic system exhibits two six-membered AgSPN-
SO rings on opposite sides of the central planar Ag2S2 core
[Ag(1)ꢀ ꢀ ꢀAg(1a) 3.753(1) Å]. The AgSPNSO ring has twisted boat
conformation, with O(1) and P(1) in apices, at 0.71 and 0.53 Å,
respectively out of the best Ag(1)S(2)N(1)S(1) plane. The coordina-
tion geometry achieved around silver is distorted tetrahedral, with
the S(1a) atom in the apex and Ag(1) atom 2.246 Å out of the O(1)/
4. Conclusions
Our studies demonstrate that anionic ligands of type [(SPPh2)-
(O2SR)N]ꢁ build easily gold(I) and silver(I) complexes. Single-
crystal X-ray diffraction studies revealed a different behavior of
the ligands substituted at sulfur with Me and C6H4Me-4 groups,
respectively, towards the gold centre. Due to the weak Auꢀ ꢀ ꢀO

352
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Acknowledgements
Financial support from the Ministry of Education and Research
of Romania (CNCSIS, Research Project No. 1456/2007-2008) is
greatly appreciated. A.P. is grateful for a research fellowship
awarded by the ‘‘Babes-Bolyai” University, Cluj-Napoca, Romania.
We warmly acknowledge the assistance of Dr. Richard Varga
(The National Center for X-ray Diffraction, ‘‘Babes-Bolyai” Univer-
sity, Cluj-Napoca, Romania) in the solid state structure
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Appendix A. Supplementary material
CCDC 711789, 711790 and 711791 contain the supplementary
crystallographic data for 4, 6 and 14ꢀ2CH2Cl2. These data can be ob-
tained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif. Supplementary
data associated with this article can be found, in the online version,
at doi:10.1016/j.ica.2009.10.022.
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