Gold and Silver Complexes with the Ligands N-[Bis(isopropoxy)-thiophosphoryl]thiobenzamide and N-[Bis(isopropoxy)thiophosphoryl]-N′-phenylthiourea

Article abstract of DOI:10.1002/ejic.200300328

Gold and silver complexes with the N-[bis(isopropoxy)-thiophosphoryl]thiobenzamide (HL¹) and N-[bis(isopropoxy)-thiophosphoryl]-N′-phenylthiourea (HL²) ligands are reported, The compounds [M(HL)(PPh³)]TfO, [Ag(HL)(TfO)] and [Ag(HL)(PPh₃)₂]TfO were obtained by the reaction of both ligands with the corresponding trifluoromethanesulfonate salts. The (acetylacetonato)gold and -silver materials [M(acac)(PPh₃)] or [Au(acac)(C₆F₅)₂] cause deprotonation of the ligands and afford [ML(PPh₃)] or [AuL(C₆F ₅)₂], whereas the reaction of [Au(TfO)(PPh₃)] with HL¹ in a 2:1 molar ratio in KOH/MeOH affords [Au ₂(L¹)(PPh₃)₂]TfO, The first homoleptic anionic metal compounds [Au^IL²]^- are also reported. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Full text of DOI:10.1002/ejic.200300328

FULL PAPER
Gold and Silver Complexes with the Ligands N-[Bis(isopropoxy)-
thiophosphoryl]thiobenzamide and N-[Bis(isopropoxy)thiophosphoryl]-
NЈ-phenylthiourea
[c]
[a]
[b]
Olga Crespo,[a,b] Vasiliy V. Brusko, M. Concepcion Gimeno, M. Loreto Tornil,
´
Antonio Laguna,*[a] and Nail G. Zabirov[c]
Keywords: Gold / Silver / Sulfur / Thiourea / Thioamide
Gold and silver complexes with the N-[bis(isopropoxy)-
thiophosphoryl]thiobenzamide (HL1) and N-[bis(isopropoxy)-
thiophosphoryl]-NЈ-phenylthiourea (HL2) ligands are re-
ported. The compounds [M(HL)(PPh3)]TfO, [Ag(HL)(TfO)]
and [Ag(HL)(PPh3)2]TfO were obtained by the reaction of
both ligands with the corresponding trifluoromethanesulfon-
ate salts. The (acetylacetonato)gold and -silver materials
[M(acac)(PPh3)] or [Au(acac)(C6F5)2] cause deprotonation of
the ligands and afford [ML(PPh3)] or [AuL(C6F5)2], whereas
the reaction of [Au(TfO)(PPh3)] with HL1 in a 2:1 molar ratio
in KOH/MeOH affords [Au2(L1)(PPh3)2]TfO. The first homo-
leptic anionic metal compounds [AuIL2]− are also reported.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2004)
Introduction
A brief overview of the chemistry with representative
elements includes the potassium derivatives in which the
metal atom is bonded to the sulfur atoms of
‘‘(OiPr)2P(S)NHC(S)Ph’’. The potassium atom can be in
the center of a diaza-18-crown-6 cycle, or as part of a more
complicated structure.[12,13] Other examples of coordination
to representative elements include the mononuclear hexaco-
ordinate compounds prepared from the reactions of differ-
ent ligands with SnCl4 although the geometries were not
confirmed by X-ray studies,[14] and the lead derivatives
[Pb{(OiPr)2P(X)NC(S)Ph}2].[15] The [M2ϩL2] stoichiometry
is the most common among the transition metal complexes
described so far (M ϭ Ni, Co, Pt, Pd, Zn, Cd)[6,7,16Ϫ22]
which have been confirmed in many cases by single-crystal
X-ray diffraction studies.
The chemistry of chelating ligands attached to metal cen-
ters through sulfur atoms has been extensively investigated.
Unusual coordination at the metal centers and interesting
stereochemistries of the chelate rings have been found.
Among them, the coordination chemistry of N-
(thiophosphoryl)thioamides or N-(thiophosphoryl)thio-
ureas has been studied and extraction of metals using
N-[bis(isopropoxy)thiophosphoryl]thiobenzamide has been
reported[1] as well as a liquid ion-selective electrode for
Hg2ϩ determination.[2] Different R1C(X)NHP(Y)R2R3 li-
gands have been reported[3Ϫ10] (R1 ϭ R-NH or NX2 X ϭ
H, alkyl or aryl group; R2, R3 ϭ alkyl, aryl, alkoxy or ary-
loxy group, X ϭ O, S; Y ϭ O, S, Se) and despite the tau-
tomeric forms in which they can exist, infrared studies on
some of them support the presence of structures in which
two double bonds CϭS and PϭS are present[7] although
delocalization of the CϪNHϪP unit has been found as
more representative of the bonding in the crystal struc-
tures[11] of PhC(S)NHP(S)(OR)2 (R ϭ iPr, Et). The species
consisting on one 1,10-diaza-18-crown-6 with two
‘‘(OiPr)2P(S)NHC(S)’’ units bonded to the nitrogen atoms
has also been described.[8]
Among the reported complexes, those containing the
coinage metals are however scarcely represented. The syn-
thesis of [Cu{PhNHC(S)NP(S)(OiPr)2}][5] and also the re-
duction of CuII to CuI with other ligands[23] such us
PhNHC(S)NHP(S)Ph2,
Me2NC(S)NHP(S)Ph2,
or
Et2NC(S)NHP(S)(OPh)2 have been described. For the lat-
ter, the crystal structure[24] consists on a trinuclear deriva-
tive of formula [Cu{Et2NC(S)NP(S)(OPh)2}]3. The three-
coordinate environment of the copper atom in
[Cu{PhC(O)NP(S)Ph2}(PPh3)][7] has also been described.
To the best of our knowledge the only such silver complex
[a]
´
´
Departamento de Quımica Inorganica, Instituto de Ciencia de
reported
is
the
tetranuclear
derivative
´
Materiales de Aragon, Universidad de Zaragoza-CSIC,
[Ag{PhC(S)NP(S)(OiPr)2}]4,[25] but no related gold com-
plexes have been described. In this paper we report the syn-
thesis and characterization of gold and silver complexes
with the N-[bis(isopropoxy)thiophosphoryl]thiobenzamide
50009 Zaragoza, Spain
[b]
[c]
´
Escuela Politecnica Superior de Huesca,
Carretera de Cuarte s/n 22071 Huesca, Spain
Kazan State University,
Kremlevskaya, st. 18, Kazan 420008, Russia
Eur. J. Inorg. Chem. 2004, 423Ϫ430
DOI: 10.1002/ejic.200300328
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
423

O. Crespo, V. V. Brusko, M. C. Gimeno, M. L. Tornil, A. Laguna, N. G. Zabirov
FULL PAPER
[PhC(S)NHP(S)(OiPr)2, HL1) and N-[bis(isopropoxy)- metal oxidation state is ϩII) and different stoichiometries
thiophosphoryl]-NЈ-phenylthiourea (PhNHC(S)NHP(S)- were obtained when the oxidation state was ϩI. In many of
(OiPr)2, HL2) ligands (see Schemes 1 and 2). The first the derivatives shown here, coordination of the ligand takes
homoleptic anionic metal compounds [AuIL2]Ϫ are also re- place without any previous deprotonation of the ligands.
ported. The previously reported derivatives are neutral (the
Results and Discussion
All the complexes described below are air and moisture
stable. The behavior of their acetone solutions corresponds
to their proposed neutral or ionic structures (Tables 1 and
2 show the conductivity values, yields, elemental analyses
for C, H, N and S, NMR and mass spectral data for all the
complexes presented). Characteristic absorptions are pre-
sent in the IR spectra of the ligands.
Thus, in HL1 the ν(NH) vibration appears at 3240 cmϪ1
and the ν(PϭS) at 648. In HL2 the ν(PϭS) vibration ap-
pears at 640 cmϪ1. Two ν(NH) vibrations appear at 3200
(PhϪNH) and 3063 cmϪ1 (CϪNHϪP), the second being
observed as a shoulder of the nujol band in the spectrum
of HL2. In the discussion we will comment on the modifi-
cation of the first band and the other band always appears
as a shoulder on the nujol band in the complexes in which
the ligand HL2 has not been deprotonated. The shifts of
the ν(PϭS) IR band and the 31P{1H} NMR resonance due
to the phosphorus atom of the ligand from those in the free
ligands point to the involvement of the sulfur atom of the
PS unit in the formation of the complexes. The shift of the
ν(NH) vibration in the SCN(H)PS unit in the complexes
which contain ligands which have not been deprotonated
Scheme 1. i) [Au(TfO)(PPh3)]/CH2Cl2, ii) [Au(TfO)(PPh3)]/KOH, could point to the formation of a six-membered chelating
MeOH, iii) 2 [Au(TfO)(PPh3)]/KOH, MeOH, iv) 1/2 PPN[Au-
ring. This is a reasonable proposal since tendency of the
(acac)2]/CH2Cl2,
1/2
PPN[AuCl2]/KOH,
MeOH,
v)
ligands to coordinate in a chelating form has already been
shown in the literature and has also been confirmed by the
X-ray structures of two of the compounds described herein.
[O{Au(PPh3)}3]ClO4/CH2Cl2,
NBu4[Au(C6F5)2]/KOH, MeOH
vi)
[Au(C6F5)2(acac)]/CH2Cl2,
Gold Complexes
The displacement of the labile trifluoromethanesulfonate
ligand in [Au(TfO)(PPh3)] affords the complexes
[Au(HL1)(PPh3)]TfO (1) and [Au(HL2)(PPh3)]TfO (2). The
vibrations corresponding to the anionic TfO groups are pre-
sent in their IR spectra [νasym(SO3) 1270, νsym(CF3) 1225,
νasym(CF3) 1151, νsym(SO3) 1033 cmϪ1].[26] In 1 the ν(NH)
absorption appears at 3242 cmϪ1 and the ν(PϭS) at 579. In
2 they appear at 3205 and 580 cmϪ1, respectively. In their
1H NMR spectra the isopropyl hydrogen atoms appear at
approximately δ ϭ 1.3 (CH3) and 5.0 (CH) ppm. The NH
hydrogen atoms of the amido-thiophosphoryl groups ap-
pear at around δ ϭ 10 (1) or 11 (2) ppm. The values in each
case are at lower fields than in the corresponding ligands
(δ ϭ 8.05 ppm HL1; 9.61 ppm HL2). In the spectrum of 2
the shift of the other NH hydrogen atom (δ ϭ 9.69 ppm)
also appears downfield of the corresponding shift in HL2
(δ ϭ 7.01 ppm).
The 31P{1H} NMR spectra show two resonances, as ex-
pected, for the two nonequivalent phosphorous atoms.
Those observed near δ ϭ 50 ppm can be assigned to the
phosphorous atoms of the HL1 or HL2 coordinated frag-
ments. In 1 the signal is δ ϭ 2.6 ppm upfield from that in
Scheme 2. i) [Ag(TfO)(PPh3)]/CH2Cl2, ii) PPh3, iii) AgTfO/CH2Cl2,
iv) 2 PPh3, v) [Ag(TfO)(PPh3)2]/CH2Cl2, vi) [Ag(TfO)(PPh3)]/KOH,
MeOH, [Ag(acac)(PPh3)]/CH2Cl2
424
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Eur. J. Inorg. Chem. 2004, 423Ϫ430

Gold and Silver Complexes with S Ligands
FULL PAPER
Table 1. Data for gold complexes 1Ϫ9
[b]
Compound
Elemental Analysis[a]
Yield
(%)
ΛM
1H NMR[c][d]
31P{1H}[c]
C
H
N
S
[Au(L1H)(PPh3)]TfO (1)
41.65 (41.5)
3.55 (3.8)
1.75 (1.5)
10.15 (10.4)
78
160
132
1.36 (br. m, 12 H, iPr-CH3), 4.95
(br. m, 2 H, iPr-CH), 7.20Ϫ7.79
(v.m., br, 20 H, Ph), 10.00
(br. s, 1 H, C-HN-P)
1.31Ϫ1.51 (v.m., br, 12 H, iPr-CH3),
4.85 (br. m, 2 H, iPr-CH),
7.20Ϫ7.38 (v.m., br, 20 H, Ph),
9.69 (br. s, 1 H, C-HN-P), 10.83
(br. s, Ph-HN)
55.1 (s),
36.9 (s)
[Au(L2 H)(PPh3)]TfO (2)
40.5 (40.85)
3.45 (3.85)
2.75 (3.0)
10.35 (10.2)
84
54.9 (s),
36.8 (s)
[Au(L1)(PPh3)] (3)
[Au(L2)(PPh3)] (4)
47.65 (48.0)
46.85 (47.1)
3.95 (4.4)
1.3 (1.8)
7.95 (8.3)
7.65 (8.1)
58
48
1
3
1.26 (br. m, 12 H, iPr-CH3), 4.76
(br. m, 2 H, iPr-CH),
7.20Ϫ7.47 (br. m, 20 H, Ph)
1.25 (br. m, 12 H, iPr-CH3), 4.73
(br. m, 2 H, iPr-CH),
55.7 (s),
37.7 (s)
4.05 (4.45)
3.15 (3.55)
54.8 (s),
37.9 (s)
7.24Ϫ7.58 (m., br, 20 H,
Ph ϩ 1 Ph-HN)
1.43 (br. m, 12 H, iPr-CH3), 4.92
(br. m, 2 H, iPr-CH),
7.18 (v.m., br, 20 H, Ph)
1.27 (br. m, 24 H, iPr-CH3), 4.83
(br. m, 4 H, iPr-CH),
7.01Ϫ7.85 (v.m., br, 40 H, Ph)
1.24 (br. m, 24 H, iPr-CH3), 4.80
(br. m, 4 H, iPr-CH),
[Au2(L1)(PPh3)2]TfO (5)
PPN[Au(L1)2] (6)
43.05 (43.4)
54.45 (54.4)
53.4 (53.85)
3.35 (3.55)
4.6 (5.0)
0.6 (1.0)
7.25 (6.95)
8.95 (9.35)
8.95 (9.25)
72
69
64
178
77
49.4 (s),
36.2 (s)
2.8 (3.05)
4.15 (4.05)
63.1 (s)
63.7 (s)
PPN[Au(L2)2] (7)
4.9 (5.05)
88
7.09Ϫ7.63 (v.m., br, 20 H, Ph),
8.52 (br. s, 2 H, Ph-HN-C)
1.25Ϫ1.48 (v.m., br, 12 H, iPr-CH3),
4.95 (br. m, 2 H, iPr-CH),
7.36Ϫ8.14 (v.m., br, 5 H, Ph)
1.39 (br. m, 12 H, iPr-CH3), 4.82
(br. m, 2 H, iPr-CH),
[Au(L1)(C6F5)2] (8)
[Au(L2)(C6F5)2] (9)
35.55 (35.45)
35.3 (34.8)
2.5 (2.25)
2.5 (2.35)
1.55 (1.65)
3.2 (3.25)
7.5 (7.55)
54
61
2
1
41.8 (s)
43.5 (s)
7.15 (7.45)
7.22Ϫ7.90 (v.m., br, 5 H,
Ph ϩ 1 Ph-HN)
[a]
[b]
[c]
[d]
Calcd. values in parentheses.
Ω
Ϫ1cm2molϪ1
.
δ in ppm. v.m. means more than one multiplet.
the free ligand and in 2 it is shifted δ ϭ 2.1 ppm downfield (31P{1H} NMR: δ: s, 33.4 ppm) were observed. Depro-
of that in free HL2. The signal in the higher field region tonation of the ligands and coordination of only one
can be assigned to the triphenylphosphane ligand. In the ‘‘Au(PPh3)’’ fragment is possible by using the starting com-
Liquid Secondary Ion Mass Spectra (LSIMS ϩ) of 2 the pound [Au(acac)(PPh3)] (acac ϭ acetylacetonate). This re-
cation molecular peak can be observed at m/z ϭ 792 (13 % action afforded [AuL1(PPh3)] (3) and [AuL2(PPh3)] (4). In
intensity), although the most intense peak corresponds to the IR spectra of the latter complexes, the ν(PϭS) vi-
the species [Au(PPh3)]ϩ (m/z ϭ 459). The cationic molecu- brations appear at 584 and 577 cmϪ1, respectively. The
lar peak was not observed in the spectrum of 1 and the ν(NH) vibrations due to the ‘‘CN(H)P’’ fragments were not
most intense peak corresponds to the species [Au(PPh3)]ϩ observed and in the spectrum of 4 the ν(NH) vibration cor-
in this case also. An observation of note is the presence in responding to the ‘‘PhNH’’ unit appears at 3293 cmϪ1. The
both spectra of the peak corresponding to [Au2L(PPh3)2]ϩ 1H NMR spectra also corroborate the observed depro-
which indicates the important stability of these species. This tonation of the ligands since no signal corresponding to the
observation led us to specifically investigate the synthesis ‘‘CN(H)P’’ fragment could be observed. In the spectrum of
of complexes of higher nuclearity. The starting compound 4 the signal corresponding to the ‘‘PhNH’’ hydrogen atom
[O{Au(PPh3)}3]ϩ is a good deprotonating agent which can overlaps with the broad signal arising from the protons of
also be used to introduce between one and three the PPh3 group. The 31P{1H} NMR spectra of 3 and 4 show
‘‘Au(PPh3)’’ fragments. The results of such reactions with similar patterns to those observed in the spectra of 1 and
both ligands in a 1:1 molar ratio are shown in Scheme 1. In 2. It is of note that the chemical shifts observed for the
both cases, the cleavage of the CϭS bond and the formation thiophosphoryl phosphorous atoms are less significant
of the corresponding N-[bis(isopropoxy)thiophosphoryl]- compared with those of the analogous nondeprotonated
benzamide [31P{1H} NMR: δ ϭ 58.7(s)ppm] or N-[bis(iso- complexes 1 and 2. The signals corresponding to the tri-
propoxy)thiophosphoryl]-NЈ-phenylurea [31P{1H} NMR: phenylphosphane ligands are shifted about 1 ppm down-
δ ϭ 58.2(s) ppm] and the gold complex [S{Au(PPh3)}3]ϩ field in both cases. In the LSIMS ϩ the molecular peaks
Eur. J. Inorg. Chem. 2004, 423Ϫ430
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425

O. Crespo, V. V. Brusko, M. C. Gimeno, M. L. Tornil, A. Laguna, N. G. Zabirov
FULL PAPER
Table 2. Data for silver complexes 10Ϫ17
[b]
Compound
Analytical data[a]
Yield ΛM
(%)
1H NMR[c][d]
31P{1H}[c]
52.2
C
H
N
S
[Ag(TfO)(L1H)] (10)
30.7 (29.3)
4.0 (3.5)
2.45 (2.45) 15.35 (16.75) 53
67
72
1.39 (br. m, 12 H, iPr-CH3),
4.89 (br. m, 2 H, iPr-CH),
7.36Ϫ8.22 (v.m., br, 5 H,
Ph ϩ 1 C-HN-P)
1.40 (br. m, 12 H, iPr-CH3),
4.88 (br. m, 2 H, iPr-CH),
7.37 (br. m, 5 H, Ph), 9.58
(br. s, 1 H, C-HN-P), 10.65
(br. s, Ph-HN)
1.37 (br. m, 12 H, iPr-CH3),
4.99 (br. m, 2 H, iPr-CH),
7.20Ϫ7.88 (m., br, 20 H, Ph),
11.57 (br. s, 1 H, C-HN-P)
1.19Ϫ1.40 (v.m., br, 12 H,
[Ag(TfO)(L2H)] (11)
29.0 (28.55)
4.0 (3.6)
4.5 (4.75)
15.05 (16.3)
78
54.0
[Ag(L1H)(PPh3)]TfO (12)
45.75 (45.95) 4.25 (4.2)
1.55 (1.65) 11.25 (11.5)
75
94
136
132
53.7 (s),
15.3 (dd),
627.4, 543.9
[Ag(L2 H)(PPh3)]TfO (13) 45.35 (45.15) 4.05 (4.25) 3.65 (3.9)
10.95 (11.3)
54.8 (s),
iPr-CH3), 4.89 (br. m, 2 H, iPr-CH), 14.5(dd),
7.20Ϫ7.38 (v.m., br, 20 H, Ph),
9.61 (br. s, 1 H, C-HN-P),
10.42 (br. s, Ph-HN)
1.33 (br. m, 12 H, iPr-CH3),
4.79 (br. m, 2 H, iPr-CH),
7.21Ϫ7.62 (v.m., br, 35 H,
Ph ϩ 1 C-HN-P)
1.38 (br. m, 12 H, iPr-CH3),
4.78 (br. m, 2 H, iPr-CH),
7.12Ϫ7.31 (v.m., br, 35 H, Ph),
9.27 (br. s, 1 H, C-HN-P),
9.83 (br. s, 1 H, Ph-HN)
1.27 (br. m, 12 H, iPr-CH3),
4.81 (br. m, 2 H, iPr-CH),
7.22Ϫ7.61 (v.m., br, 20 H, Ph)
1.21Ϫ1.49 (v.m., br, 12 H,
iPr-CH3), 4.72 (br. m, 2 H,
iPr-CH), 6.94Ϫ7.68 (v.m., br,
20 H, Ph) ϩ 1 Ph-HN)
617.9, 535.7
[Ag(L1H)(PPh3)2]TfO (14) 54.2 (54.65)
[Ag(L2H)(PPh3)2]TfO (15) 53.8 (53.9)
4.35 (4.6)
4.45 (4.6)
1.1 (1.25)
2.4 (2.5)
7.3 (8.75)
85
84
155
140
54.5 (s),
7.3 (br)
7.44 (8.65)
54.9 (s),
6.1 (dd),
409.8, 360.0
[Ag(L1)(PPh3)] (16)
[Ag(L2)(PPh3)] (17)
53.65 (54.25) 4.8 (5.0)
1.95 (2.05) 9.05 (9.35)
66
54
1
1
57.1 (s),
14.1 (dd),
570.3, 494.7
58.4 (s),
52.65 (53.05) 4.45 (5.05) 3.55 (4.0)
8.75 (9.15)
14.3 (br)
[a]
[b]
[c]
[d]
Theoretical values in brackets.
Ω
Ϫ1cm2molϪ1
.
δ in ppm. v.m. means more than one multiplet.
appear at m/z ϭ 776 (16 %) (3) and 791 (8 %) (4). The In fact, the LSIMS ϩ shows a peak corresponding to the
reaction of HL1 or HL2 with [Au(TfO)(PPh3)] in a 1:1 mo- species [Au2L2(PPh3)2] (m/z ϭ 1249, 28 %) and the pro-
lar ratio in MeOH with a stoichiometric amount of KOH posed structure is shown in Scheme 1.
affords 3 or 4. The reaction in a 1:2 molar ratio of HL1
We have also investigated the reactivity of these ligands
with
[Au(TfO)(PPh3)]
in
KOH/MeOH
affords towards PPN[Au(acac)2] in a molar ratio of 2:1. The result-
[Au2L1(PPh3)2]TfO (5). In the IR spectrum of 5 the vi- ant compounds PPN[Au(L1)2] (6) and PPN[Au(L2)2] (7)
brations corresponding to the anionic trifluoromethanesul- show ν(PϭS) bands at 610 and 578 cmϪ1, respectively. In 7
fonate are observed and the ν(PϭS) band appears at 579 the ν(NH) vibration appears at 3302 cmϪ1. The H NMR
1
cmϪ1. The ligand deprotonation is confirmed by the ab- spectra show the phenyl and isopropyl protons and in the
sence of the NH vibration in the IR spectrum and an analy- case of compound 7 the NH hydrogen atom appears at δ ϭ
1
sis of the H NMR spectrum in which only those absorp- 8.52 ppm. Two signals are present in their 31P{1H} NMR
tions corresponding to the isopropyl and phenyl groups are spectra. The resonance at approximately δ ϭ 63 ppm can be
observed. The 31P{1H} NMR spectrum display two signals, assigned to the thiophosphoryl group which shows a very
that at δ ϭ 49.9 ppm can be assigned to the phosphorus significant downfield shift from the signals of the ligands.
atom of the thiophosphoryl group with the other (a broad The other signal at δ ϭ 21.2 ppm corresponds to the PPN
signal) corresponding to the triphenylphosphane ligands. cation. The anionic molecular peak of compound 6 is pre-
The cationic molecular peak is present in the LSIMS ϩ sent in the LSIMS Ϫ (m/z ϭ 829, 85 %). Although no struc-
(m/z ϭ 1234, 52 %). The same reaction with HL2 affords tural confirmation has been obtained by X-ray crystallogra-
a solid, the 31P{1H} NMR spectrum of which displays five phy, a homoleptic mononuclear derivative has been pro-
signals. The most intense resonance corresponds to the posed. More complicated arrangements consisting of more
[S{Au(PPh3)}3]ϩ cation and two of the signals which ap- that one ‘‘[AuL2]ϩ’’ unit could give rise to the same conduc-
pear with very weak intensities at 54.9 and 37.0 ppm poss- tivity and elemental analysis values but are considered to
ibly correspond to the analog of 5 i.e. [Au2L2(PPh3)2]TfO. be much less probable. Based on the probable chelate mode
426
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Gold and Silver Complexes with S Ligands
FULL PAPER
of the ligand and the results of similar studies with other In the 1H NMR spectra, resonances arising from the hydro-
metals we are inclined to favor a tetra-coordinated arrange- gen atoms of the NH groups bonded to the thiophosphoryl
ment as the most likely structure.
groups are shifted to low field from those of the free li-
The syntheses of gold() complexes derived from [Au- gands. An additional signal is present in 13 at δ ϭ 9.61 ppm
(acac)(C6F5)2] have also been carried out. The resultant due to the hydrogen atom of the NH urea unit. In the
products, [Au(C6F5)2(L1)] (8) and [Au(C6F5)2(L2)] (9), show 31P{1H} NMR spectra the two nonequivalent phosphorus
ν(PϭS) vibrations at 567 and 591 cmϪ1, respectively, and in atoms display resonances with different shapes. One of
9 the ν(NH) vibration appears at 3403 cmϪ1. The vibrations them, assigned to the thiophosphoryl group, is a narrow
corresponding to the pentafluorophenyl rings are also pre- resonance which appears at about δ ϭ 54 ppm while the
sent at around 1508, 964 and 784 cmϪ1. In both derivatives other is broad and corresponds to the triphenylphosphane
the deprotonation of the ligands is evident from the 1H ligand. When the spectra were recorded at Ϫ55 °C the
NMR spectra. Very notable high field shifts from the values broad resonances split into two doublets as a consequence
in the free ligands were observed in the 31P{1H} spectra of the phosphorus atom coupling to the two silver isotopes,
for both complexes (see Table 1). The 19F spectra show the 107Ag and 109Ag. The LSIMS ϩ show the cationic molecu-
presence of two nonequivalent pentafluorophenyl rings, lar peaks in both cases [m/z ϭ 686, 28 % (12); 704, 31 %
five signals were observed in the ratio of (13)].
1(Fp):1(Fp):2(Fo):2(Fo):4(Fm). The signal at approximately
Like 12 and 13, complexes 14 and 15 can also be ob-
δ ϭ Ϫ160 ppm corresponds to the meta fluorine atoms. The tained by reaction of the ligands with [Ag(TfO)(PPh3)2] in
fluorine atoms in the para- and ortho-positions give rise to a 1:1 molar ratio. In their IR spectra the ν(PϭS) vibrations
two triplets at around δ ϭ Ϫ158 ppm and two multiplets at appear at 571 (14) and 573 (15) cmϪ1, and those arising
approximately δ ϭ Ϫ121 ppm, respectively. The molecular from the NH groups come at 3280 (14) and 3220 (15) cmϪ1
peaks are present in the LSIMS ϩ at m/z ϭ 848 (24 %) (8) In the H NMR spectra of 15 both the NH resonances can
.
1
and 863 (42 %; 9).
be observed whereas in 14 the resonance of the hydrogen
atom of the NH group is obscured by the phenyl hydrogen
resonances. The 31P{1H} NMR spectra show the same pat-
Silver Complexes
The reaction of AgTfO with both ligands in a molar ratio terns observed for 12 and 13 but only in the case of 15 the
of 1:1 afforded the complexes [Ag(TfO)(HL1)] (10) and broad signal becomes split at low temperature (even at
[Ag(TfO)(HL2)] (11). Their conductivity values in acetone Ϫ85 °C). For these four-coordinate complexes the reson-
solution are between those described for the presence of no ances due to the triphenylphosphane ligands appear near
electrolyte and a 1:1 electrolytic species. This is due to the δ ϭ 7 ppm which is upfield of those in the three-coordinate
lability of the trifluoromethanesulfonate anion. In their IR analogs. The structure of both complexes have been ana-
spectra the vibrations corresponding to the presence of co- lyzed by X-ray studies which reveal the expected four-coor-
valent TfO[26] groups are present [νasym(SO3) 1283 and dination (tetrahedral geometry) around the silver center
1240, νsym(CF3) 1220, νasym(CF3) 1180, νsym(SO3) 1030 (Figure 1, Figure 2). In compound 14 the ring defined by
cmϪ1]. The ν(NH) and ν(PϭS) vibrations appear at 3290, Ag(1), S(1), P(1), N(1), C(1) and S(2) adopts a boat confor-
1
575 (10) or 3270, 598 (11) cmϪ1. In the H NMR spectrum mation in which the angle between the planes defined by
of 10 the NH hydrogen atom bonded to the thiophosphoryl S(1), P(1), Ag(1), S(2) and P(1), N(1), C(1), S(2) is 53.7°.
group is coincidental with the multiplet which corresponds Compound 15 shows a twist boat conformation in which
to the phenyl protons whereas in 11, it appears at δ ϭ the atoms S(1), Ag(1), S(2) and C(1) lie in the same plane.
10.65 ppm. The other NH proton in 11 shows a resonance Similar AgϪP bond lengths (Tables 2 and 3) can be ob-
at δ ϭ 9.58 ppm. Their 31P{1H} NMR spectra both display served in both complexes which vary from 2.4712(8) to
˚
one singlet near δ ϭ 50 ppm. These resonances are shifted 2.4909(7) A. The shortest values of those found in
[27]
˚
upfield by δ ϭ 5.5 ppm in (10) and downfield by δ ϭ [Ag(dppe)2]NO3 [2.488(3)Ϫ2.527(3) A]
are very close to
1.2 ppm in (11) from those of the free ligands. The LSIMS those in 14 and 15 and also those found in
ϩ of complex 11 shows the cationic molecular peak [Ag(phen){(PPh2)2C2B10H10}]ClO4
[2.463(2),
2.479(2)
[28]
[Ag(HL2)]ϩ at m/z ϭ 441 (47 %).
A].
Longer
values
have
been
found
in
˚
Displacement of the trifluoromethanesulfonate anion [Ag{(SPPh2)2CH2}{(PPh2)2C2B10H10}]ClO4
[2.526(2),
[28]
˚
and deprotonation in 10 and 11 allows the synthesis of dif- 2.532(2) A]
and in [Ag(PPh3)4]ClO4 (1 ϫ 2.650(2), 3 ϫ
Two different AgϪS bond lengths are pre-
[29]
˚
ferent complexes. Thus, the reaction with triphenylphos- 2.668(5) A].
phane in a 1:1 or 1:2 molar ratio affords the three-coordi- sent in each complex, the distances to the sulfur atoms of
nate [Ag(HL1)(PPh3)]TfO (12), [Ag(HL2)(PPh3)]TfO (13) the thiophosphoryl groups are longer [2.6952(8) A (14),
˚
or four-coordinate [Ag(HL1)(PPh3)2]TfO (14) and 2.6648(8) (15) A] than the other Ag-S distances [2.5892(2)
˚
[Ag(HL2)(PPh3)2]TfO (15) complexes. Compounds 12 and A (14), 2.5379(8) (15) A] in both complexes (Table 4). These
13 can also be obtained by reaction of the ligands with values can be compared with those found in other tetra-
˚
˚
[Ag(TfO)(PPh3)] in a 1:1 molar ratio. In their IR spectra hedral silver complexes such as [AgBr(18S6)] (18S6
ϭ
the vibrations corresponding to the TfO- anion are present 1,4,7,10,13,16-hexathiacyclooctadecane) [2.514(1)Ϫ2.636(1)
[30]
and those due to ν(PϭS) appear at 575 (12) and 574 cmϪ1 A],
[Ag{(SPPh2)2CH2}{(PPh2)2C2B10H10}]ClO4
˚
[28]
(13). The NH bands appear at 3260 (12) or 3220 (13) cmϪ1
.
[2.540(2), 2.588(2) A],
[Ag{S2C2(CN)2}(PPh3)4][31]
˚
Eur. J. Inorg. Chem. 2004, 423Ϫ430
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 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
427

O. Crespo, V. V. Brusko, M. C. Gimeno, M. L. Tornil, A. Laguna, N. G. Zabirov
FULL PAPER
˚
˚
[2.568(7), 2.653(7) A], or in [Ag4(µ3-SC2B10H11)2(µ-
O3SCF3)2(PPh3)2][32] [two tetrahedral, two trigonal silver
atoms, Ag(tetrahedral)ϪS distances 2.5467(14), 2.6508(14)
Table 4. Bond lengths [A] and angles [°] for 15
Ag(1)ϪP(2) 2.4510(8) P(2)ϪC(41)
Ag(1)ϪP(3) 2.4808(8) P(2)ϪC(21)
Ag(1)ϪS(2) 2.5379(8) P(3)ϪC(51)
Ag(1)ϪS(1) 2.6648(8) P(3)ϪC(71)
1.816(3)
1.820(3)
1.820(3)
1.824(3)
1.827(3)
1.682(3)
1.368(4)
1.336(4)
1.422(4)
˚
A].
P(1)ϪO(1)
P(1)ϪO(2)
P(1)ϪN(1) 1.674(3)
P(1)ϪS(1)
1.557(2)
1.562(2)
P(3)ϪC(61)
S(2)ϪC(1)
N(1)ϪC(1)
1.9390(10) N(2)ϪC(1)
P(2)ϪC(31) 1.814(3)
N(2)ϪC(11)
P(2)ϪAg(1)ϪP(3)
P(2)ϪAg(1)ϪS(2)
P(3)ϪAg(1)ϪS(2)
P(2)ϪAg(1)ϪS(1)
P(3)ϪAg(1)ϪS(1)
S(2)ϪAg(1)ϪS(1)
118.51(3) O(1)ϪP(1)ϪO(2)104.35(11)
113.46(3) O(1)ϪP(1)ϪN(1)102.18(12)
114.78(3) O(2)ϪP(1)ϪN(1)99.64(12)
111.39(3) O(1)ϪP(1)ϪS(1) 116.81(8)
98.05(3) O(2)ϪP(1)ϪS(1) 113.93(8)
97.08(2) N(1)ϪP(1)ϪS(1) 117.63(10)
The syntheses of deprotonated derivatives have been car-
ried out by two synthetic routes just as for the gold com-
plexes. The first is the use of (acac)Ϫ as a deprotonating
agent, the other using methanol and KOH. The reactions
afford [AgL1(PPh3)] (16) or [AgL2(PPh3)] (17). In the IR
spectrum of 17 the ν(PϭS) vibration appears at 575 cmϪ1
and the ν(NH) at 3203 cmϪ1. Due to a poor mixture be-
tween 16 and Nujol, no satisfactory IR spectrum for 16
could be recorded. The deprotonation of the ligands is evi-
Figure 1. Molecular structure of the cation of compound 14; hydro-
gen atoms have been omitted for clarity
1
dent from the H NMR spectra. Moreover, two resonances
are present in the 31P{1H} NMR spectra and only in the
case of compound 16, the broad signal is split into two
doublets.
Conclusions
The reactions studied indicate that a great variety of co-
ordination types and complexes can be prepared
(Schemes 1 and 2). Some notable points are a) The use of
acetylacetonate as a suitable deprotonating agent. This is a
new synthetic pathway that allows the use of solvents other
than alcohols. The mixture MeOH/KOH, widely described
in the literature, may not be the best since some metallic
fragments may not be soluble in alcohol. b) The
[Ag(HL)(TfO)] compounds synthesized are interesting
starting materials which allow the incorporation of the
‘‘Ag(HL)’’ unit (also deprotonated) into more complicated
structures. c) Cleavage of the CϭS bond occurs upon the
reaction of the oxonium salt [O{Au(PPh3)}3] with the li-
gands.
Figure 2. Molecular structure of the cation of compound 15; hydro-
gen atoms have been omitted for clarity
˚
Table 3. Selected bond lengths [A] and angles [°] for 14
Ag(1)ϪP(2)
Ag(1)ϪP(3)
Ag(1)ϪS(1)
Ag(1)ϪS(2)
S(1)ϪP(1)
2.4711(8)
2.4907(7)
2.5893(7)
2.6954(7)
N(1)ϪC(1)
N(1)ϪP(1)
P(1)ϪO(2)
P(1)ϪO(1)
1.355(3)
1.685(2)
1.550(2)
1.556(2)
1.666(3)
1.9440(10) S(2)ϪC(1)
Experimental Section
P(2)ϪAg(1)ϪP(3) 116.11(2)
P(2)ϪAg(1)ϪS(1) 117.50(2)
P(3)ϪAg(1)ϪS(1) 115.56(2)
P(2)ϪAg(1)ϪS(2) 117.29(2)
C(1)ϪS(2)ϪAg(1) 114.36(10)
Reagents: AgTfO and PPh3 were purchased from Aldrich and were
used as received. The ligands (HL1)[4] and (HL2)[5] and the starting
materials [Au(acac)(PPh3)],[33] [O{Au(PPh3)}3]ClO4,[34] [Au-
C(1)ϪN(1)ϪP(1)
O(2)ϪP(1)ϪO(1)
O(1)ϪP(1)ϪN(1)
O(2)ϪP(1)ϪS(1)
O(1)ϪP(1)ϪS(1)
N(1)ϪP(1)ϪS(1)
128.2(2)
106.61(11)
99.81(11)
112.25(8)
115.66(9)
114.52(9)
(acac)(C6F5)2],[35]
PPN[Au(acac)2],[33,36]
[Ag(TfO)(PPh3)],[37]
P(3)ϪAg(1)ϪS(2)
S(1)ϪAg(1)ϪS(2)
P(1)ϪS(1)ϪAg(1)
90.74(2)
94.48(2)
92.47(3)
[Ag(TfO)(PPh3)2][37] were synthesized according to literature meth-
ods. [Au(TfO)(PPh3)] was synthesized from [AuCl(PPh3)][38] and
AgTfO in dichloromethane.
428
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Eur. J. Inorg. Chem. 2004, 423Ϫ430

Gold and Silver Complexes with S Ligands
FULL PAPER
General Procedures: Infrared spectra were recorded on
a
0.0610 g) in methanol (20 mL). After stirring for 15 min the solvent
was reduced to about 5 mL. Addition of n-hexane (20 mL) led to
precipitation of a yellow (3) or white (4) solid.
PerkinϪElmer FT-IR Spectrum 1000 spectrophotometer in the
range 4000Ϫ400 cmϪ1 using Nujol mulls between polyethylene
sheets. Conductivities were measured in (ca. 5 ϫ 10Ϫ4)  acetone Method b: HL1 (0.1 mmol, 0.032 g) or HL2 (0.1 mmol, 0.033 g) was
solutions with a Jenway 4010 conductimeter. Elemental analyses
added to a solution of [Au(acac)(PPh3)] (0.1 mmol, 0.056 g) in di-
of C, H, N and S were carried out with a PerkinϪElmer 240C chloromethane. After stirring for 15 min the solution was filtered
microanalyzer. Mass spectra were recorded on a VG Autospec in-
through celite and the filtrate concentrated to about 5 mL. Ad-
dition of n-hexane (20 mL) led to precipitation of a yellow (3) or
white (4) solid. Recrystallization from dichloromethane/hexane af-
forded the pure compounds.
strument using the LSIMS (ϩ, Ϫ) techniques and nitrobenzyl al-
1
cohol as a matrix and on an HP59987 A ELECTROSPRAY. H,
19F and 31P NMR spectra were recorded on a Bruker ARX 300
spectrometer in CDCl3 or (CD3)2CO. Chemical shifts are quoted
relative to external SiMe4 (1H), CFCl3 (19F) or 85 % H3PO4 (31P).
[Au2(L1)(PPh3)2]TfO (5): KOH (0.1 mmol, 0.006 g) and HL1
(0.1 mmol, 0.032 g) were added to a solution of [Au(TfO)(PPh3)]
(0.2 mmol, 0.121 g) in methanol (20 mL). After stirring for 15 min
the solvent was concentrated to about 5 mL. Addition of n-hexane
(20 mL) led to precipitation of a yellow solid (5). Recrystallization
from dichloromethane/hexane afforded the pure compound.
Syntheses: [Au(HL)(PPh3)]TfO [L ؍ L1(1), L2(2)]: HL1 (0.1 mmol,
0.032 g) or HL2 (0.1 mmol, 0.033 g) was added to a dichlorometh-
ane solution (20 mL) of [Au(TfO)(PPh3)] (0.1 mmol, 0.0610 g).
After stirring for 15 min the solvent was reduced to about 5 mL.
Addition of n-hexane (20 mL) led to precipitation of an orange (1)
or white (2) solid. Recrystallization from dichloromethane/hexane
afforded the pure compounds.
PPN[Au(L)2] [L ؍ L1(6), L2 (7)]: HL1 (0.2 mmol, 0.064 g) or HL2
(0.2 mmol, 0.066 g) was added to a solution of PPN[Au(acac)2]
(0.1 mmol, 0.093 g) in dichloromethane (20 mL). After stirring for
15 min the solution was filtered through celite and the filtrate con-
centrated to about 5 mL. Addition of n-hexane (20 mL) led to pre-
cipitation of a pale yellow (6) or brown (7) solid. Recrystallization
from dichloromethane/hexane afforded the pure compounds.
[Au(L)(PPh3)] [L ؍ L1(3), L2(4)] Method a: KOH (0.1 mmol,
0.006 g) and then HL1 (0.1 mmol, 0.032 g) or HL2 (0.1 mmol,
0.033 g) was added to a solution of [Au(TfO)(PPh3)] (0.1 mmol,
[Au(C6F5)2(L)] [L ؍ L1 (8), L2 (9)]: HL1 (0.1 mmol, 0.032 g) or HL2
(0.1 mmol, 0.033 g) was added to a solution of [Au(C6F5)2(acac)]
(0.1 mmol, 0.063 g) in dichloromethane (20 mL). The stirred solu-
tion was filtered through celite and the filtrate concentrated to
about 5 mL. Addition of n-hexane (20 mL) led to precipitation of
a yellow solid (8 or 9). Recrystallization from dichloromethane/
hexane afforded the pure compounds. 19F NMR for 8: δ ϭ Ϫ160
(m, m-F, 4F), 156 (t, p-F, 3J(FF) 20.0 Hz), 155.7 (t, p-F, 3J(FF)
19.8 Hz), Ϫ121.9 (m, o-F, 2F), Ϫ121.7 (m, o-F, 2F) ppm. 19F NMR
for 9: δ ϭ Ϫ161.8 (m, m-F, 4F), 157.2 (t, p-F, 3J(FF) 20.0 Hz),
Table 5. Details of data collection and structure refinement for 14
and 15
Compound
14
15
Chemical formula C50H50AgF3NO5P3S3 C50H51AgF3N2O5P3S3
Crystal habit
Crystal size (mm) 0.5 ϫ 0.2 ϫ 0.14
colorless prism
yellow tablet
0.32 ϫ 0.28 ϫ 0.2
triclinic
Crystal system
Space group
monoclinic
P21/c
22.0613(19)
12.8679(11)
18.8993(16)
90
113.755(1)
90
4910.6(7)
4
¯
P1
˚
a (A)
12.9484(18)
13.3524(19)
15.831(2)
71.895(2)
79.351(3)
76.764(2)
2513.3(6)
2
3
˚
b (A)
156.8 (t, p-F, J(FF) 19.6 Hz), Ϫ122.4 (m, o-F, 2F), Ϫ122.1 (m, o-
F, 2F).
˚
c (A)
α (°)
β (°)
γ (°)
[Ag(HL)(TfO)] [L ؍ L1 (10), L2 (11)]: HL1 (0.1 mmol, 0.032 g) or
HL2 (0.1 mmol, 0.033 g) was added to a dichloromethane solution
(20 mL) of Ag(TfO) (0.1 mmol, 0.026 g). After stirring for 4 hours
the solvent was reduced to about 5 mL. Addition of n-pentane
(20 mL) led to precipitation of a yellow (10) or white (11) solid.
Recrystallization from dichloromethane/pentane afforded the pure
compounds.
3
˚
V (A )
Z
Dc (g cmϪ3
Mr
)
1.486
1098.87
2256
1.472
1113.89
1144
F(000)
T (°C)
Ϫ100
58
0.695
Ϫ100
56
0.680
2θmax (°)
[Ag(HL)(PPh3)]TfO [L ؍ L1 (12), L2 (13)] Method a: PPh3
(0.1 mmol, 0.026 g) was added to a solution of [Ag(HL)(TfO)]
(0.1 mmol; L1 0.057 g, L2 0.058 g) in dichloromethane (20 mL).
After stirring for 15 min the solvent was concentrated to about
5 mL. Addition of n-hexane (20 mL) led to precipitation of a yellow
(12) or white (13) solid.
µ(Mo-Kα) (mmϪ1
)
No. of reflections 31073
measured
16548
No. of unique
reflections
Rint
11287
11100
0.0769
0.0500
0.0386
0.0446
0.1006
11100
R1[a] [F Ͼ 4σ(F)]
Method b: HL1 (0.1 mmol, 0.032 g) or HL2 (0.1 mmol, 0.033 g) was
added to a solution of [Ag(TfO)(PPh3)] (0.1 mmol, 0.052 g) in di-
chloromethane (20 mL). The stirred solution was concentrated to
about 5 mL. Addition of n-hexane (20 mL) led to precipitation of
a yellow (12) or white (13) solid. Recrystallization from dichloro-
methane/hexane afforded the pure compounds.
wR2[b](F2, all refl.) 0.1322
No. of reflections 11287
used
616
0
0.983
1.222
[Ag(HL)(PPh3)2]TfO [L ؍ L1 (14), L2 (15)] Method a: PPh3
(0.2 mmol, 0.053 g) was added to a solution of [Ag(HL)(TfO)]
(0.1 mmol; L1 0.057 g, L2 0.058 g) in dichloromethane (20 mL).
After stirring for 15 min the solvent was concentrated to about
5 mL. Addition of n-hexane (20 mL) led to precipitation of a yellow
(14) or white (15) solid.
[a]
[b]
2
2 2
R1 (F) ϭ Σ||Fo| Ϫ |Fc||/Σ|Fo|.
wR2 (F2) ϭ [Σ{w(Fo Ϫ Fc 2) }/
Σ{w(Fo ) }]0·5; wϪ1 ϭ σ2(Fo ) ϩ (aP)2 ϩ bP, where P ϭ [Fo
ϩ
2 2
2
2
[c]
2Fc ]/3 and a and b are constants adjusted by the program. S ϭ
[Σ{w(Fo Ϫ Fc ) }/(n Ϫ p)]0·5, where n is the number of data and p
2
2 2
the number of parameters.
Eur. J. Inorg. Chem. 2004, 423Ϫ430
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 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
429

O. Crespo, V. V. Brusko, M. C. Gimeno, M. L. Tornil, A. Laguna, N. G. Zabirov
FULL PAPER
[10]
Method b: HL1 (0.1 mmol, 0.032 g) or HL2 (0.1 mmol, 0.033 g) was
added to a solution of [Ag(TfO)(PPh3)2] (0.1 mmol, 0.078 g) in di-
chloromethane (20 mL). The stirred solution was concentrated to
about 5 mL. Addition of n-hexane (20 mL) led to precipitation of
a yellow (14) or white (15) solid. Recrystallization from dichloro-
methane/hexane afforded the pure compounds.
R. M. Kamalov, M. G. Zimin, A. N. Pudovik, Usp. Khim. 1985,
54, 2044Ϫ2075.
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Method b: HL1 (0.1 mmol, 0.032 g) or HL2 (0.1 mmol, 0.033 g) was
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X-ray Crystallographic Study: The crystals were mounted in inert
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˚
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tropically. CCDC 203107 and 203108 contain the supplementary
crystallographic data for this paper. These data can be obtained
free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or
from the Cambridge Crystallographic Data Center, 12, Union
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We thank the Direccion General de Investigacion no. BQU2001-
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Russian Foundation for Basic Research (no. 03-03-32372a and
03-03-96225r2003tatarstan-0).
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Published Online November 4, 2003
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