Table 4 Selected bond lengths [Å] and angles [Њ] for complex 12
Materials
The starting materials Fc(SPh)2,5 Fc(SePh)2,5 [Au(C6F5)3-
(OEt2)]21 were prepared by published procedures. [Au(OTf )-
(PPh3)] was obtained by reaction of [AuCl(PPh3)]22 with
Ag(OTf ) in dichloromethane and [Ag(OTf )(PPh3)] by reaction
of Ag(OTf ) with PPh3 in diethyl ether. All other chemicals used
were commercially available and used without further
purification.
Ag–P
Ag–O(1)
2.443(3)
2.473(12)
Ag–Se(2)
Ag–Se(1)
2.645(2)
2.7347(18)
P–Ag–O(1)
P–Ag–Se(2)
O(1)–Ag–Se(2)
P–Ag–Se(1)
O(1)–Ag–Se(1)
Se(2)–Ag–Se(1)
C(11)–Se(1)–Ag
108.7(4)
124.12(11)
94.1(4)
119.34(10)
95.8(3)
107.58(6)
106.1(3)
C(1)–Se(1)–Ag
C(6)–Se(2)–Ag
C(21)–Se(2)–Ag
C(51)–P–Ag
C(41)–P–Ag
C(31)–P–Ag
S–O(1)–Ag
100.1(4)
105.5(5)
107.7(5)
114.6(5)
112.2(4)
114.3(4)
132.7(8)
Syntheses
Synthesis of [Au(PPh3){Fc(XPh)2}]OTf (X ؍
S (3), Se (4)).
To a solution of [Fc(XPh)2] (0.040 g, 0.1 mmol, 3; 0.049 g,
0.1 mmol, 4) in 20 mL of dichloromethane was added the
corresponding amount of [Au(OTf )(PPh3)] (0.061 g, 0.1 mmol)
and the mixture stirred for 15 min. Concentration of the solu-
tion to ca. 5 mL and addition of diethyl ether (10 mL) gave
complexes 3 and 4 as orange solids. Complex 3: Yield 76%.
ΛM 117 ΩϪ1 cm2 molϪ1. Elemental analysis (%). Found: C,
49.98; H, 3.54; S, 9.45. Calc. for C41H33AuF3FeO3S3: C, 50.41;
1
H, 3.37; S, 9.80. 31P{1H}, δ: 34.2 (s) ppm. H, δ: 7.5–7.1 (m,
25H, C6H5), 4.52 (m, 8H, C5H4) ppm. Complex 4: Yield 54%.
ΛM 108 ΩϪ1 cm2 molϪ1. Elemental analysis (%). Found: C,
45.52; H, 2.74; S, 2.75. Calc. for C41H33AuF3FeO3SSe2: C, 45.85;
H, 3.07; S, 2.98. 31P{1H}, δ: 34.8 (s) ppm. 1H, δ: 7.59–7.12
(m, 25H, C6H5), 4.55 (m, 8H, C5H4) ppm.
Synthesis of [{Au(C6F5)3}2{Fc(XPh)2}] (X ؍
S (5), Se (6)).
To a solution of [Fc(XPh)2] (0.040 g, 0.1 mmol, 5; 0.049 g,
0.1 mmol, 6) in 20 mL of dichloromethane was added [Au-
(C6F5)3(OEt2)] (0.154 g, 0.2 mmol) and the mixture stirred for
15 min. Concentration of the solution to ca. 5 mL and addition
of hexane (10 mL) gave complexes 5 or 6 as orange solids.
Complex 5: Yield 57%. ΛM 0.5 ΩϪ1 cm2 molϪ1. Elemental
analysis (%). Found: C, 38.98; H, 1.33; S, 3.61. Calc. for
Fig. 4 Perspective view of complex 12, with the atom labelling scheme;
H atoms are omitted for clarity.
to the triphenylphosphine and the oxygen atom of the triflate.
The angles Se(1)–Ag–Se(2) and O(1)–Ag–P are very regular,
107.58(6) and 108.7(4)Њ, whereas the O(1)–Ag–Se(2) and P–Ag–
Se(1) angles are 94.1(4) and 119.34(10)Њ, respectively. The
Ag–Se bond distances are also somewhat dissimilar, 2.645(2)
and 2.7347(18) Å, and slightly longer than those found in com-
pound 8, but of the same order as those found in selenoether
derivatives.20
1
C58H18Au2F30FeS2: C, 38.71; H, 1.00; S, 3.56. H, δ: 7.63–7.43
(m, 10H, C6H5), 4.06 (m, 4H, C5H4), 3.94 (m, 4H, C5H4) ppm.
19F, δ: Ϫ121.8 (m, 8F, o-F), Ϫ122.3 (m, 4F, o-F), Ϫ155.9 [t, 4F,
3
3
p-F, J(FF) 20 Hz], Ϫ156.0 [t, 2F, p-F, J(FF) 20 Hz], Ϫ160.5
(m, 8F, m-F), Ϫ160.9 (m, 4F, m-F) ppm. Complex 6: Yield 70%.
ΛM 0 ΩϪ1 cm2 molϪ1. Elemental analysis (%). Found: C, 37.14;
1
H, 1.17. Calc. for C58H18Au2F30FeSe2: C, 36.78; H, 0.95. H,
Complexes 7 and 8 possess a weakly coordinated ligand in
trifluoromethanesulfonate and thus can react further with other
ligands such as 1,10-phenanthroline (phen) to give the com-
plexes [Ag(phen){Fc(XPh)2}]OTf OTf (X = S (13), Se (14)),
presumably with the silver centres in a tetrahedral geometry.
Complexes 13 and 14 are orange and moisture-stable solids that
behave as 1 : 1 electrolytes in acetone solutions.
δ: 7.61–7.30 (m, 10H, C6H5), 4.32 (s, 1H, C5H4), 4.23 (s, 1H,
C5H4), 4.13 (s, 1H, C5H4), 4.10 (s, 1H, C5H4), 4.02 (s, 1H, C5H4),
3.98 (s, 1H, C5H4), 3.94 (s, 1H, C5H4), 3.63 (s, 1H, C5H4) ppm.
19F, δ: Ϫ121.2 (m, 8F, o-F), Ϫ122.4 (m, 4F, o-F), Ϫ155.8 [t, 4F,
3
3
p-F, J(FF) 20 Hz], Ϫ155.9 [t, 2F, p-F, J(FF) 20 Hz], Ϫ160.4
(m, 8F, m-F), Ϫ161.0 (m, 4F, m-F) ppm.
The 1H NMR spectra of 13 and 14 present only two
multiplets for the phenyl and cyclopentadienyl protons and four
signals for the phenanthroline protons. In the mass spectra
(LSIMSϩ) the cation molecular peaks appear at m/z = 691
(19%, 13) and 785 (14%, 14), respectively.
Synthesis of [Ag(OTf ){Fc(XPh)2}] (X ؍
S (7), Se (8)). To a
solution of [Fc(XPh)2] (0.040 g, 0.1 mmol, 7; 0.049 g, 0.1 mmol,
8) in 20 mL of dichloromethane was added the corresponding
amount of [Ag(OTf )] (0.026 g, 0.1 mmol) and the mixture
stirred for 30 min. Concentration of the solution to ca. 5 mL
and addition of diethyl ether (10 mL) gave complexes 7 and 8 as
orange solids. Complex 7: Yield 84%. ΛM 10 ΩϪ1 cm2 molϪ1
.
Experimental
Elemental analysis (%). Found: C, 41.23; H, 2.40; S, 13.92.
Instrumentation
1
Calc. for C23H18AgF3FeO3S3: C, 41.50; H, 2.70; S, 14.43. H,
Infrared spectra were recorded on a Perkin-Elmer 883 spectro-
photometer, over the range 4000–200 cmϪ1, using Nujol mulls
between polyethylene sheets. Conductivities were measured in
ca. 5 × 10Ϫ4 mol dmϪ3 solutions with a Philips 9509 conducti-
meter. C, H, and N analyses were carried out with a Perkin-
Elmer 2400 microanalyser. Mass spectra were recorded on a VG
Autospec, with the liquid secondary-ion mass spectra (LSIMS)
technique, using 3-nitrobenzyl alcohol as matrix. NMR spectra
were recorded on a Varian UNITY 300 or Bruker ARX 300
apparatus in CDCl3 solutions. Chemical shifts are quoted rel-
δ: 7.5–7.18 (m, 10H, C6H5), 4.51 (m, 4H, C5H4), 4.48 (m, 4H,
C5H4) ppm. Complex 8: Yield 63%. ΛM 2 ΩϪ1 cm2 molϪ1
.
Elemental analysis (%). Found: C, 36.01; H, 2.30; S, 4.03.
1
Calc. for C23H18AgF3FeO3SSe2: C, 36.65; H, 2.39; S, 4.25. H,
δ: 7.22–7.18 (m, 10H, C6H5), 4.46 (m, 8H, C5H4) ppm.
Synthesis of [Ag{Fc(XPh)2}2](OTf ) (X ؍
S (9), Se (10)). To a
solution of [Fc(XPh)2] (0.080 g, 0.2 mmol, 9; 0.098 g, 0.2 mmol,
10) in 20 mL of dichloromethane was added the corresponding
amount of [Ag(OTf )] (0.026 g, 0.1 mmol) and the mixture
stirred for 30 min. Concentration of the solution to ca. 5 mL
and addition of diethyl ether (10 mL) gave complexes 9 or 10 as
1
ative to SiMe4 (external, H), CFCl3 (19F, external), and 85%
H3PO4 (external, 31P).
J. Chem. Soc., Dalton Trans., 2002, 2250–2255
2253