Synthesis of gold ferrocenyl substituted ylides and methanides: Crystal structure of [FcCH(AuPPh3)PPh3]ClO4 [Fc=(η5-C5H5)Fe(η5-C 5H4)]

Article abstract of DOI:10.1016/s0020-1693(99)00038-9

The treatment of [FcCH₂NMe₃]I with tertiary or ditertiary phosphines gives the phosphonium salts [FcCH₂PR₃]I (PR₃=PPh₃, PPh₂Me) or [FcCH₂PPh₂CH₂P

Full text of DOI:10.1016/s0020-1693(99)00038-9

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Inorganica Chimica Acta 291 (1999) 60–65
Synthesis of gold ferrocenyl substituted ylides and methanides:
crystal structure of [FcCH(AuPPh3)PPh3]ClO4
[Fc=(h5-C5H5)Fe(h5-C5H4)]
Eva M. Barranco, M. Concepcio´n Gimeno, Antonio Laguna *
Departamento de Qu´ımica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n, Uni6ersidad de Zaragoza-CSIC, 50009 Zaragoza, Spain
Received 22 September 1998
Abstract
The treatment of [FcCH2NMe3]I with tertiary or ditertiary phosphines gives the phosphonium salts [FcCH2PR3]I (PR3=PPh3,
PPh2Me) or [FcCH2PPh2CH2PPh2]I. The reaction of [FcCH2PR3]ClO4 with [Au(acac)(PPh3)] gives the ylide complexes
[FcCH(AuPPh3)PR3]ClO4. The compound [FcCH2PPh2CH2PPh2]OTf reacts with several gold(I) complexes to give
[FcCH2PPh2CH2PPh2(AuCl)]OTf, [FcCH2PPh2CH2PPh2(AuC6F5)]OTf or [FcCH2PPh2CH2PPh2(AuPPh3)](OTf)2. The reaction of
[FcCH2PPh2CH2PPh2]ClO4 with [O(AuPPh3)3]ClO4 leads to the methanide type species [FcCH2PPh2C(AuPPh3)2PPh2(AuPPh3)]-
(ClO4)2. © 1999 Elsevier Science S.A. All rights reserved.
Keywords: Gold complexes; Ferrocenyl complexes; Methanide complexes; Ylide complexes
complexes of gold have been previously reported and
reviewed but no examples with ferrocene moieties have
1. Introduction
been described.
Ferrocene derivatives containing phosphorus groups
have been the object of great attention in recent years
[1]. Amongst them, the chemistry of 1,1%-bis(diphenyl-
phosphino)ferrocene and its metal complexes has been
extensively developed [2]. However, other derivatives in
2. Experimental
which the phosphorus atom is not directly bonded to
the cyclopentadienyl ring are far less studied. The syn-
thesis of the phosphonium salts [FcCH2PR3]I [3] or the
mixed phosphonium–phosphine salt [FcCH2PPh2-
CH2PPh2]I [4] was reported some years ago. However,
the coordination chemistry of these compounds has not
been studied and only some sodium or potassium
methanide complexes have been described.
Here we report on the reactivity of these phospho-
nium salts with several gold complexes. Thus, some
ylide or methanide derivatives are synthesised and the
crystal structure of the compound [FcCH(AuPPh3)-
PPh3]ClO4 is described. Ylide [5] and methanide [6]
2.1. General procedure
Infrared spectra were recorded in the range 4000–200
cm−1 on a Perkin–Elmer 883 spectrophotometer using
Nujol mulls between polyethylene sheets. Conduc-
tivities were measured in ca. 5×10−4 mol dm−3 solu-
tions with a Philips 9509 conductimeter. C, H and
S analyses were carried out with a Perkin–Elmer 2400
microanalyzer. Mass spectra were recorded on a
VG Autospec, with the liquid secondary ion mass
spectrometry (LSIMS) technique, using nitrobenzyl al-
cohol as the matrix. NMR spectra were recorded on a
Varian Unity 300 spectrometer and a Bruker ARX 300
spectrometer in CDCl3. Chemical shifts are cited rela-
tive to SiMe4 (1H, external) and 85% H3PO4 (31P,
external).
* Corresponding author. Tel.: +34-976-761185; fax: +34-976-
761187.
E-mail address: alaguna@posta.unizar.es (A. Laguna)
0020-1693/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S0020-1693(99)00038-9

E.M. Barranco et al. / Inorganica Chimica Acta 291 (1999) 60–65
61
2.2. Preparation of the compounds
dichloromethane (20 ml) was added [Au(acac)(PPh3)]
(0.059 g, 0.1 mmol) and the solution was stirred for 2 h.
Evaporation of the solvent to ca. 5 ml and addition of
diethyl ether (20 ml) afforded yellow solids of 4 or 5.
Complex 4, yield 66%. Anal. Calc. for C47H40Au-
ClFeO4P2: C, 55.39; H, 3.95. Found: C, 54.89; H, 3.88%.
The compounds [FcCH2PR3]I (PR3=PPh3, PPh2Me)
[3], [FcCH2PPh2CH2PPh2]I [4], [Au(acac)(PPh3)] [7],
[O(AuPPh3)3]ClO4 [8], [AuCl(tht)] [9] and [Au(C6F5)-
(tht)] [10] were prepared by published procedures.
[Au(OTf)(PR3)] was obtained by reaction of equimolar
amounts of [AuCl(PPh3)] [11] and Ag(OTf).
1
LM 119.6 V−1 cm2 mol−1. H NMR, l: 3.82 (m, 2H,
C5H4), 4.0 (m, 2H, C5H4), 4.06 (s, 5H, C5H5), 4.3 (m,
1H, CH), 7.2–7.6 (m, br, 30H, Ph). 31P{1H} NMR, l:
23.8 (m, 1P, CHPPh3), 39.9 (m, 1P, AuPPh3) ppm.
Complex 5, yield 71%. Anal. Calc. for C42H38Au-
ClFeO4P2: C, 52.71; H, 4.00. Found: C, 53.11; H, 4.39%.
2.2.1. [FcCH2PR3]ClO4 (PR3=PPh3 (1), PPh2Me (2))
To
a
dichloromethane solution (30 ml) of
[FcCH2PPh3]I (0.353 g, 0.6 mmol) or [FcCH2PPh2Me]I
(0.315 g, 0.6 mmol) was added Ag(ClO4) (0.124 g, 0.6
mmol). The mixture was stirred for 2 h and then the
solid AgI formed was filtered. The solution was concen-
trated to ca. 5 ml and diethyl ether (20 ml) was added
to yield yellow solids of 1 or 2. Compound 1, yield 86%.
Anal. Calc. for C29H26ClFeO4P: C, 62.11; H, 4.67.
Found: C, 61.87; H, 4.37%. LM 130 V−1 cm2 mol−1. 1H
NMR, l: 3.90 (m, 2H, C5H4), 4.06 (m, 2H, C5H4), 4.30
(s, 5H, C5H5), 4.61 [d, 2H, CH2, J(PH) 12.3 Hz],
7.2–7.6 (m, br, 15H, Ph). 31P{1H} NMR, l: 19.8 (s)
ppm. Compound 2, yield 87%. Anal. Calc. for
C24H24ClFeO4P: C, 57.80; H, 4.85. Found: C, 57.34; H,
4.68%. LM 135.5 V−1 cm2 mol−1. 1H NMR, l: 2.37 (m,
br, 3H, PMe), 4.07–4.24 (m, br, 11H, FcCH2), 7.64–
7.74 (m, 10H, Ph). 31P{1H} NMR, l: 19.6 (s) ppm.
1
LM 156 V−1 cm2 mol−1. H NMR, l: 2.27 [d, 3H,
J(PH) 12.61 Hz, PMe], 4.04 (m, 2H, C5H4), 4.06 (m, 2H,
C5H4), 4.07 (s, 5H, C5H5), 4.18 [d, 1H, CH, J(PH) 12.0
Hz], 7.2–7.8 (m, br, 25H, Ph). 31P{1H} NMR, l: 21.6
[d, 1P, J(PP) 9.2 Hz, CHPPh2Me), 40.7 (d, 1P, AuPPh3)
ppm.
2.2.4. [FcCH2PPh2CH2PPh2(AuX)]OTf (X=Cl (6),
C6F5 (7))
To a solution of [FcCH2PPh2CH2PPh2]OTf (0.073 g,
0.1 mmol) in dichloromethane (20 ml) was added [Au-
Cl(tht)] (0.032 g, 0.1 mmol) or [Au(C6F5)(tht)] (0.045 g,
0.1 mmol) and the mixture was stirred for 1 h. Evapora-
tion of the solvent to ca. 5 ml and addition of diethyl
ether (15 ml) gave complexes 6 or 7 as yellow solids.
Complex 6, yield 72%. Anal. Calc. for C37H33AuClF3-
FeO3P2S: C, 46.05; H, 3.44; S, 3.32. Found: C, 45.89; H,
2.2.2. [FcCH2PPh2CH2PPh2]X (X=ClO4 (3a), OTf
(3b))
1
3.23; S, 3.56%. LM 95.8 V−1 cm2 mol−1. H NMR, l:
To a solution of [FcCH2PR2CH2PPh2]I (0.710 g, 1
mmol) in dichloromethane (30 ml) was added Ag(ClO4)
(0.207 g, 1 mmol) or Ag(OTf) (0.026 g, 0.1 mmol) and
the mixture was stirred for 2 h. Then the solid AgI was
filtered and the solution concentrated to ca. 5 ml.
Addition of diethyl ether (20 ml) gave a yellow solid of
3a or 3b. Compound 3a: yield 95%. Anal. Calc. for
C36H33ClFeO4P2: C, 63.32; H, 4.87. Found: C, 62.98; H,
3.92 (m, br, 2H, CH2), 4.08 (m, br, 2H, CH2), 4.26 (m,
br, 9H, Fc), 7.3–7.9 (m, br, 20H, Ph). 31P{1H} NMR,
l: 17.7 (m, br, 1P), 19.0 (m, br, 1P) ppm. Complex 7,
yield 86%. Anal. Calc. for C43H33AuF8FeO3P2S: C,
47.10; H, 3.03; S, 2.92. Found: C, 47.43; H, 3.21; S,
1
3.26%. LM 114 V−1 cm2 mol−1. H NMR, l: 3.89 (m,
2H, C5H4), 4.06 (m, 2H, C5H4), 4.22 (s, 5H, C5H5), 4.36
[d, 2H, CH2, J(PH) 13.2 Hz], 4.41 [d, 2H, CH2, J(PH)
12.3 Hz], 7.2–7.8 (m, br, 20H, Ph). 31P{1H} NMR, l:
19.6 (m, 1P, C–P–C), 25.5 [d, 1P, P–Au, J(PP) 9 Hz]
ppm. 19F NMR, l: −116.7 (m, 2F, o-F), −157.4 [t,
1F, p-F, J(FF) 19.9 Hz], −162.1 (m, 2F, m-F).
1
4.55%. LM 140 V−1 cm2 mol−1. H NMR, l: 3.66 [d,
2H, CH2, J(PH) 13.91 Hz], 3.85 (m, 2H, C5H4), 3.96 (m,
2H, C5H4), 4.23 (s, 5H, C5H5), 4.41 [d, 2H, CH2, J(PH)
11.53 Hz], 7.2–7.6 (m, br, 20H, Ph). 31P{1H} NMR, l:
21.6 [d, 1P, C–P–C, J(PP) 50 Hz], −27.3 (d, 1P, C–P).
Compound 3b: yield 78%. Anal. Calc. for
C37H33F3FeO3P2S: C, 60.67; H, 4.54; S, 4.38. Found: C,
2.2.5. [FcCH2PPh2CH2PPh2Au(PPh3)](OTf)2 (8)
60.36; H, 4.55; S, 4.39%. LM 120 V−1 cm2 mol−1. H
To a solution of [FcCH2PR2CH2PPh2]OTf (0.073 g,
0.1 mmol) in dichloromethane (20 ml) was added
[Au(OTf)(PPh3)] (0.061 g, 0.1 mmol) and the mixture
was stirred for 1 h. Concentration of the solution to ca.
5 ml and addition of diethyl ether afforded a yellow solid
of 8. Yield 95%. Anal. Calc. for C56H48AuF6FeO6P3S2:
C, 50.16; H, 3.60; S, 4.78. Found: C, 49.62; H, 3.31; S,
1
NMR, l: 3.84 [d, 2H, CH2, J(PH) 14.4 Hz], 4.0 (m, 2H,
C5H4), 4.05 (m, 2H, C5H4), 4.19 (s, 5H, C5H5), 4.49 [d,
2H, CH2, J(PH) 12.1 Hz], 7.2–7.6 (m, br, 20H, Ph).
31P{1H} NMR, l: 23.3 [d, 1P, C–P–C, J(PP) 62.9 Hz],
−28.2 (d, 1P, C–P).
1
2.2.3. [FcCH(AuPPh3)PR3]ClO4 (PR3=PPh3 (4),
PPh2Me (5))
To a solution of [FcCH2PPh3]ClO4 (0.056 g, 0.1
4.87%. LM 150 V−1 cm2 mol−1. H NMR, l: 4–5 ppm
(br, overlapped, 9H, Fc+CH2), 7–8 (m, br, 35H, Ph).
31P{1H} NMR, ABX system, lX 20.0 (m, 1P, C–P–C),
lA 31.0, lB 44.2 ppm (P–Au–P), J(AB) 326 Hz.
mmol) or [FcCH2PPh2Me]ClO4 (0.050 g, 0.1 mmol) in

62
E.M. Barranco et al. / Inorganica Chimica Acta 291 (1999) 60–65
Table 1
2.2.6. [FcCH2PPh2C(AuPPh3)2PPh2Au(PPh3)](ClO4)2
(9)
Details of data collection and structure refinement for complex 4
To a solution of [FcCH2PPh2CH2PPh2]ClO4 (0.068 g,
0.1 mmol) in dichloromethane (20 ml) was added
[O(AuPPh3)3]ClO4 (0.149 g, 0.1 mmol) and the mixture
was stirred for 2 h. Concentration of the solution to ca.
5 ml and addition of diethyl ether (10 ml) led to a
yellow solid of 9. Yield 86%. Anal. Calc. for
C90H76Au3Cl2FeO8P5: C, 50.09; H, 3.55. Found: C,
Empirical formula
Formula weight
C47H40AuClFeO4P2
1019
P21/c
4124.6(7)
4
1.641
10.9310(10)
32.850(4)
11.8070(10)
103.381(7)
173
Space group
3
,
V(A )
Z
Dcalc (g cm−3
)
,
a (A)
,
b (A)
1
49.87; H, 3.54%. LM 199 V−1 cm2 mol−1. H NMR, l:
,
c (A)
i (°)
T (K)
3.41 [d, 2H, CH2, J(PH) 12.1 Hz, CH2–P], 3.88 (s, 5H,
C5H5), 3.98 (m, 2H, C5H4), 4.24 (m, 2H, C5H4), 7–8
(m, br, 65H, Ph). 31P{1H} NMR, ABM2X system, lA
45.6, lB 53.3 (P–Au–P), J(AB) 317 Hz, lM 36.2 (m,
2P, PPh3), lX 28.3 (m, 1P, C–P–C) ppm.
v(Mo Ka) (mm−1
Ra (F, F\4|(F))
)
4.091
0.0526
0.159
wRb(F2, all reflections)
a R(F)=SꢀꢀFoꢀ−ꢀFcꢀꢀ/SꢀFoꢀ.
b wR(F2)=[S{w(Fo2−Fc2)2}/S{w(Fo2)2}]0.5
.
2.3. X-ray structure determination of complex 4
the methylene protons. Compound 2 also shows a
doublet for the phosphine methyl protons. The 31P{1H}
NMR spectra present one singlet for the phosphorus
atom.
Crystals of 4 were grown from dichloromethane/hex-
ane. A yellow prism of 0.55×0.25×0.20 mm was
mounted in inert oil on a glass fibre. A total of 9910
intensities were registered using monochromated Mo
,
Ka radiation (u=0.71073 A, 2qmax=50°) on a Siemens
We have also prepared the compound [FcCH2PPh2-
CH2PPh2]X (X=ClO4 (3a), OTf (3b)) by reaction of
the previously known [FcCH2PPh2CH2PPh2]I with
Ag(ClO4) or Ag(OTf) (Scheme 1). Compound 3a also
shows in its IR spectrum the absorptions of the
P4 four circle diffractometer; 7033 unique reflections
(Rint=0.0848) and 6983 were used for all calculations.
Cell constants were refined from setting angles of 60
reflections in the range 2q=10–25°. An absorption
correction based on C-scans was applied, with trans-
mission factors 0.760–0.941. The structure was solved
by direct methods and all the atoms were refined an-
isotropically on F2 using the program SHELXL-93 [12].
H atoms were included using a riding model. The final
wR(F2) was 0.159 for all reflections, with a conven-
tional R(F) of 0.0526, for 505 parameters. S=1.035;
perchlorate anion at 1095 (vs, br) and 623 (m) cm−1
,
whereas 3b shows the absorptions of the triflate
anion at 1265(vs, br) [was(SO3)], 1223(s) [ws(CF3)],
1
1150(s) [was(CF3)] and 1023(s) [ws(SO3)] cm−1. The H
NMR spectrum presents two multiplets for the a and b
protons of thesubstituted Cp and a singlet for the
protons of the unsubstituted Cp ring and a doublet for
each methylene group. Surprisingly, no coupling with
max. Dz=1.674 e A−3. Further details are shown in
,
Table 1.
3. Results and discussion
The reaction of [FcCH2NMe3]I with tertiary phosphi-
nes affords the previously synthesised phosphonium
salts [FcCH2PR3]I (PR3=PPh3, PPh2Me). In order to
react them with gold complexes we have changed the
anion iodide to perchlorate by reacting [FcCH2PR3]I
with AgClO4 (Scheme 1). The new compounds
[FcCH2PR3]ClO4 (PR3=PPh3 (1), PPh2Me (2)) are air
and moisture stable yellow solids that behave as 1:1
electrolytes in acetone solutions. Their IR spectra show
the bands arising from the phosphine and ferrocenyl
groups and those of the perchlorate anion around 1100
1
(vs, br) and 620 (m) cm−1. In their H NMR spectra
appear two multiplets for the a and b protons of the
substituted cyclopentadienyl group, a singlet for the
protons of the unsubstituted Cp ring and a doublet for
Scheme 1. (i) PR3, (ii) PPh2CH2PPh2, (iii) Ag(ClO4), (iv) Ag(ClO4) or
Ag(OTf).

E.M. Barranco et al. / Inorganica Chimica Acta 291 (1999) 60–65
63
one of the phosphorus atoms is observed for the P–CH2–
P group, but a doublet was also observed in the starting
material [FcCH2PPh2CH2PPh2]I [4]. In the 31P{1H}
NMR spectrum two doublets for the two phosphorus
atoms with coupling between them appear. The chemical
shift is characteristic of a phosphonium phosphorus,
:21 ppm, and uncoordinated phosphine ligand, : −27
ppm.
The treatment of the phosphonium salts 1 or 2 with
[Au(acac)(PPh3)] leads to complexes [FcCH(AuPPh3)-
PR3]ClO4 (PR3=PPh3 (4), PPh2Me (5)) originated by
substitution of one proton of the methylene group by the
isolobal fragment AuPPh3+; acetylacetone is formed in
the reaction (Eq. 1).
Fig. 1. Structure of the cation of complex 4 in the crystal showing the
atom-numbering scheme. Radii are arbitrary. The Cp and Ph hydro-
gen atoms are omitted for clarity.
(1)
The use of acetylacetonato (acac) complexes has been
previously reported in the synthesis of ylide and
methanide gold derivatives [13–15]. Complexes 4 and 5
are air and moisture stable yellow solids that behave as
1:1 electrolytes in acetone solutions.
moieties, as do the Fe–C distances. In some gold or silver
complexes with ferrocene derivatives as ligands, we have
observed the presence of weak h2 interactions between
the metal centres and two of the carbons of the cyclopen-
tadienyl ring [17,18]. In this complex, the Au···C(1) and
In the 1H NMR spectrum of 4 and 5 the protons of the
substituted cyclopentadienyl ring appear as two multi-
plets, the protons of the unsubstituted Cp ring appear as
a singlet, whereas the CH proton appears as a doublet of
doublets in complex 4 as a consequence of the coupling
with both phosphorus atoms and as a doublet for
complex 5. The methyl protons in 5 appear also as a
doublet. The 31P{1H} NMR spectra show two doublets
for the two different phosphorus environments with
coupling between them.
,
Au···C(5) distances are around 3.5 A and, thus, although
very weak, point out the existence of possible bonding
interaction.
We have also studied the reaction of compound 3b
with several gold complexes. First, the treatment of 3b
with [AuR(tht)] (tht=tetrahydrothiophene), which pos-
sesses the labile ligand tht, leads to the gold complexes
[FcCH2PPh2CH2PPh2(AuR)]OTf (R=Cl (6), C6F5 (7))
by coordination of the gold centre to the phosphine
phosphorus atom. Complexes 6 and 7 are yellow solids,
In the liquid secondary positive-ion mass spectra the
cationic molecular peaks appear at m/z=919 (4, 15%)
and 857 (5, 71%); the fragments arising from the loss of
PPh3 are also present at 657 (4, 90%) and 594 (5, 6%).
The molecular structure of complex 4 has been con-
firmed by an X-ray diffraction study and the cation is
shown in Fig. 1. A selection of bond lengths and angles
are collected in Table 2. The gold atom has a linear
geometry with an almost ideal angle of 178.2(3)°. The
Table 2
,
Selected bond lengths (A) and angles (°) for 4
Au–C(11)
P(1)–C(41)
P(1)–C(21)
P(2)–C(71)
P(2)–C(51)
2.089(9)
1.802(9)
1.810(10)
1.818(10)
1.824(11)
Au–P(2)
2.274(3)
1.807(9)
1.811(8)
1.821(11)
1.503(13)
P(1)–C(31)
P(1)–C(11)
P(2)–C(61)
C(1)–C(11)
C(11)–Au–P(2)
178.2(3)
C(41)–P(1)–C(31)
C(31)–P(1)–C(21)
C(31)–P(1)–C(11)
C(71)–P(2)–C(61)
C(61)–P(2)–C(51)
C(61)–P(2)–Au
108.7(4)
105.4(4)
111.0(4)
106.0(5)
105.4(5)
113.4(3)
110.9(6)
108.3(4)
118.4(9)
116.3(7)
119.2(7)
122.9(8)
118.5(8)
122.8(8)
C(41)–P(1)–C(21) 110.6(4)
C(41)–P(1)–C(11) 111.7(4)
C(21)–P(1)–C(11) 109.4(5)
C(71)–P(2)–C(51) 107.2(5)
C(71)–P(2)–Au
C(51)–P(2)–Au
C(1)–C(11)–Au
C(26)–C(21)–P(1) 120.9(8)
C(32)–C(31)–P(1) 124.0(8)
C(42)–C(41)–P(1) 121.8(7)
C(56)–C(51)–P(2) 118.4(9)
C(66)–C(61)–P(2) 123.4(9)
C(76)–C(71)–P(2) 118.7(8)
,
Au–C distance is 2.089(9) A and is of the same order as
those found in other ylide or methanide complexes such
,
as [Au(C6F5)2{m-(PPh2)2CH(AuC6F5)}] (2.094(7) A) [16].
112.5(4)
111.9(4)
119.9(6)
,
The Au–P bond distance of 2.274(3) A is similar to
C(1)–C(11)–P(1)
P(1)–C(11)–Au
complexes which have a carbon ligand trans to the
phosphorus.
C(22)–C(21)–P(1)
C(36)–C(31)–P(1)
C(46)–C(41)–P(1)
C(52)–C(51)–P(2)
C(62)–C(61)–P(2)
C(72)–C(71)–P(2)
The cyclopentadienyl rings are staggered by 10°
around the Cp···Cp axis defined by the torsion angle
C(1)–centre–centre–C(8). The distances of the Fe atom
,
to the centres of the rings are 1.651 and 1.659 A which
compare well with the values reported for other ferrocene

64
E.M. Barranco et al. / Inorganica Chimica Acta 291 (1999) 60–65
Scheme 2. (i) X=OTf, [AuCl(tht)] or [Au(C6F5)(tht)], (ii) X=OTf, [Au(OTf)(PPh3)], (iii) X=ClO4, [O(AuPPh3)3]ClO4.
air and moisture stable that behave as 1:1 electrolytes in
acetone solutions. Their IR spectra show the presence of
the w(Au–Cl) band at 335 (m) cm−1 and the bands
assigned to a pentafluorophenyl group bonded to Au(I)
Finally, we have synthesised a methanide gold deriva-
tive, [FcCH2PPh2C(AuPPh3)2PPh2(AuPPh3)](ClO4)2 (9),
by reacting [FcCH2PPh2CH2PPh2]ClO4 with [O-
(AuPPh3)3]ClO4 (Scheme 2); the oxonium salt has al-
ready proved to be a good deprotonating agent in the
synthesis of gold complexes. The most acidic methylene
protons, which are those in between both phosphorus
atoms, are removed and substituted by the isolobal
fragment AuPPh3+. Complex 9, with a different counte-
rion, can also be obtained by treatment of 8 with two
equivalents of [Au(acac)(PPh3)]. Compound 9 is a pale-
yellow air and moisture stable solid that behaves as
electrolyte 1:2 in acetone solutions. Its IR spectrum
shows, in addition to the bands arising at the ferrocene
and phenyl groups, the w(Au–C) vibration at 536 (w)
cm−1. In the 1H NMR spectrum, the methylene protons
appear as a doublet, the a and b protons of the C5H4
ring as multiplets and the C5H5 protons as a singlet. The
31P{1H} NMR spectrum presents an ABM2X system.
Again the AB part corresponds to the PPh2–Au–PPh3
unit. The signals of the B nuclei appear as multiplets
because the coupling with M and/or X nuclei and the
signals of M and X are multiplets. In the LSIMS+
mass spectrum, the molecular peak does not appear but
the fragment due to the loss of one ClO4− anion does at
m/z=2057 (12%) with coincident experimental and
calculated isotopic distribution.
1
at 1504 (s), 955 (s) and 793 (m) cm−1. In the H NMR
spectra, the resonances of the methylene groups appear
as doublets for complex 7, whereas in 6 there are broad
singlets. The resonances of the ferrocene moiety appear
as two multiplets and a singlet in the appropriate 2:2:5
ratio. The 31P{1H} NMR spectra show two signals
corresponding to two different phosphorus environ-
ments; for complex 7 the signals are better resolved and
appear as doublets. The 19F spectrum of 7 presents three
resonances for the ortho, meta and para fluorines of the
pentafluorophenyl group.
In the positive liquid secondary ion mass spectra
(LSIMS+) of complexes 6 and 7 the molecular peaks
appear at m/z=815 (6, 68%) and 947 (7, 100%).
The reaction of 3b with [Au(OTf)(PPh3)] leads to the
dicationic complex [FcCH2PPh2CH2PPh2(AuPPh3)]-
(OTf)2 (8) in high yield. Complex 8 is an air and
moisture stable yellow solid that behaves as a 1:2
1
electrolyte in acetone solutions. Its H NMR spectrum
shows broad resonances (even when the experiment is
carried out at low temperature) between 4 and 5 ppm
which correspond to the methylene and ferrocenyl pro-
tons. The 31P{1H} NMR spectrum presents an ABX
system. The AB part corresponds to the PPh2–Au–
PPh3 unit, with a large coupling constant of 326 Hz.
In the LSIMS+ mass spectrum, the molecular peak
appears at m/z=1340 (7%), although with low inten-
sity. However, the fragments at m/z=1191 (12%) and
1041 (100%) due to the loss of one or two triflate anions
are more intense.
4. Supplementary material
Tables listing crystallographic data, positional and
thermal parameters, and complete bond lengths and

E.M. Barranco et al. / Inorganica Chimica Acta 291 (1999) 60–65
65
[6] A. Laguna, M. Laguna, J. Organomet. Chem. 394 (1990) 743.
[7] (a) D. Gibson, B.F.G. Johnson, J. Lewis, J. Chem. Soc., A
(1970) 367. (b) J. Vicente, M.T. Chicote, Inorg. Synth. 32
(1998) 172.
angles for complex 4 are available from the authors on
request.
[8] A.N. Nesmeyanov, E.G. Perevalova, Yu.T. Struchkov, M.Yu.
Antipin, K.I. Grandberg, V.P. Dyadchenko, J. Organomet.
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[9] R. Uso´n, A. Laguna, M. Laguna, Inorg. Synth. 26 (1989) 85.
[10] R. Uso´n, A. Laguna, J. Vicente, J. Chem. Soc., Chem. Com-
mun. (1976) 353.
Acknowledgements
We thank the Direccio´n General de Investigacio´n
Cient´ıfica y Te´cnica (No. PB97-1010-C02-01) and the
Fonds der Chemischen Industrie for financial support.
[11] R. Uso´n, A. Laguna, Inorg. Synth. 21 (1982) 71.
[12] G.M. Sheldrick, SHELXL-93: Program for Crystal Structure
Refinement, University of Go¨ttingen, Germany, 1993.
[13] J. Vicente, M.T. Chicote, M.C. Lagunas, Inorg. Chem. 32
(1993) 3748 and Refs. therein.
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