New reagents for the synthesis of a series of ferrocenoyl functionalized copper and silver chalcogenolate complexes

Article abstract of DOI:10.1039/b804597f

A series of silylated ferrocenoyl chalcogenide reagents, FcC(O)ESiMe ₃ (E = S, Se, Te; Fc = ferrocene), can be prepared in very good yield from FcC(O)Cl and LiESiMe₃. These reagents are used in the preparation of triphenylphosphine-ligated copper and silver ferrocenoyl thiolate and selenolate complexes, [M₄(E{O}CFc)₄(PPh ₃)₄], (M = Cu, Ag; E = S, Se) and [Cu₂(μ- Se{O}CFc)₂(PPh₃)₃] from solubilized copper(i) and silver(i) acetate. The structures of these complexes have been determined via single-crystal X-ray diffraction. The driving force for these reactions is the thermodynamically favorable formation and elimination of AcOSiMe ₃. The synthesis and characterization of both starting reagents and cluster complexes are discussed. The Royal Society of Chemistry 2008.

Full text of DOI:10.1039/b804597f

View Article Online / Journal Homepage / Table of Contents for this issue
PAPER
www.rsc.org/dalton | Dalton Transactions
New reagents for the synthesis of a series of ferrocenoyl functionalized copper
and silver chalcogenolate complexes†
Daniel G. MacDonald and John F. Corrigan*
Received 18th March 2008, Accepted 18th June 2008
First published as an Advance Article on the web 6th August 2008
DOI: 10.1039/b804597f
A series of silylated ferrocenoyl chalcogenide reagents, FcC(O)ESiMe3 (E = S, Se, Te; Fc = ferrocene),
can be prepared in very good yield from FcC(O)Cl and LiESiMe3. These reagents are used in the
preparation of triphenylphosphine-ligated copper and silver ferrocenoyl thiolate and selenolate
complexes, [M4(E{O}CFc)4(PPh3)4], (M = Cu, Ag; E = S, Se) and [Cu2(l-Se{O}CFc)2(PPh3)3] from
solubilized copper(I) and silver(I) acetate. The structures of these complexes have been determined via
single-crystal X-ray diffraction. The driving force for these reactions is the thermodynamically
favorable formation and elimination of AcOSiMe3. The synthesis and characterization of both starting
reagents and cluster complexes are discussed.
Introduction
Results and discussion
The synthesis of cluster complexes containing multiple fer-
rocene units has been the focus of attention in many research
groups recently.1 This interest stems, in part, from the unique
electrochemical properties the complexes exhibit as well as the po-
tential applications of these materials in molecular electronics and
chemical sensors.2 Recent efforts have also been devoted to the in-
corporation of multiple ferrocene units into polymers,3 aromatic,4
dendrimeric5 frameworks and inorganic cores.6 Silylated chalco-
gen reagents have been shown to offer a controlled route to
the formation of structurally characterized metal–chalcogenolate
clusters and nanoclusters which are monodisperse in nature.7 Sim-
ilarly, metal–chalcogenolate supported multiferrocene assemblies
are readily prepared in a reaction involving a silylated ferrocene–
chalcogen reagent and a metal salt.8 These silylated reagents
react readily with metal salts, through the thermodynamically
favorable formation of XSiMe3 (X = Cl, OAc), to form metal–
chalcogenolate (RE−) bonds. In addition, the soluble XSiMe3 does
not impede the formation and crystallization of the nanometer
sized cluster complexes. The tunability of the “R” substituent
presents the opportunity to easily control the characteristics of the
surface of the generated particles. These reagents can be tailored
to introduce specific chemical functionalities onto the surface of
the cluster.8 Herein we describe the synthesis and characterization
of a series of ferrocenoyl chalcogenides, FcC(O)ESiMe3 (E = S,
Se, Te) 1a, 1b, and 1c and their application in the preparation
of polyferrocene functionalized metal–chalcogenolate complexes
2–6.
The silylated ferrocenoyl chalcogenides 1a, b, and c are readily
prepared in good yield from the reaction of ferrocenoylchloride9
with lithio(trimethylsilyl)–chalcogenolate10 (Scheme 1). When
LiSSiMe3 or LiSeSiMe3 was added to a stirred solution of
FcC(O)Cl in Et2O at 0 ◦C, compound 1a or 1b were isolated
as a red or blood red oil, respectively. The tellurolate 1c can be
prepared at −40 ◦C and isolated as a brown oil. Compounds
1a, 1b and 1c all decompose readily in the presence of air and
are susceptible to decomposition over time, even when stored
cold and under inert atmosphere. In addition to decomposition
in air, 1c also is sensitive to ambient light. The 1H NMR
spectrum of 1a shows three well resolved peaks at 4.16, 4.51
and 4.95 ppm and a singlet at 0.48 ppm, the latter corresponding
to the protons of the trimethylsilyl moiety. For both the Se (1b)
1
and Te (1c) analogs the H NMR spectra display the same four
characteristic peaks, although they are shifted downfield relative
to those observed for 1a. Due to the instability of reagents 1a–1c
elemental analysis could not be obtained, although high reso-
lution mass spectrometry confirmed the chemical formula. These
ferrocenoyl chalcogenides are excellent precursors for the synthesis
of metal–chalcogenolate complexes. Unlike ferrocenecarboxylate
ligands (FcC(O)O−) which can bond to Cu or Ag through both
oxygen atoms in a bidentate fashion,11 reagents 1a, 1b bond
exclusively through the sulfur or selenium atom (vide infra).
When one equivalent of 1a is reacted with one equivalent of
Department of Chemistry, The University of Western Ontario, London,
Ontario, Canada N6A 5B7. E-mail: corrigan@uwo.ca; Fax: +1-519-661-
3022; Tel: +1-519-661-2111 ext. 86387
† Electronic supplementary information (ESI) available: A plot of the
molecular structure of 5. CCDC reference numbers 681444–681448. For
ESI and crystallographic data in CIF or other electronic format see DOI:
10.1039/b804597f
Scheme 1
5048 | Dalton Trans., 2008, 5048–5053
This journal is
The Royal Society of Chemistry 2008
©

View Article Online
◦
◦
˚
˚
Table 2 Selected bond lengths (A) and angles ( ) for 3
Table 1 Selected bond lengths (A) and angles ( ) for 2
Cu(1)–S(1)
Cu(1)–P(1)
Cu(1)–P(2)
S(1)–Cu(1)–P(1)
S(1)–Cu(1)–P(2)
P(1)–Cu(1)–P(2)
2.2432(9)
2.2614(8)
2.2510(8)
115.05(3)
120.82(3)
124.08(3)
Cu(1)–Se(1)
Cu(1)–Se(2)
Cu(2)–Se(1)
Cu(2)–Se(2)
Cu(1)–P(1)
Cu(2)–P(2)
Cu(2)–P(3)
Cu(1)–Cu(2)
C(11)–O(1)
2.3962(8)
2.4140(8)
2.5640(8)
2.5474(8)
2.2366(14)
2.2571(13)
2.2655(13)
2.6265(9)
1.209(6)
P(1)–Cu(1)–Se(2)
116.31(4)
Se(1)–Cu(1)–Se(2)
P(1)–Cu(1)–Se(1)
Se(2)–Cu(2)–Se(1)
P(2)–Cu(2)–P(3)
Se(1)–Cu(2)–P(2)
Se(2)–Cu(2)–P(3)
121.07(3)
121.97(5)
110.04(3)
124.23(5)
94.39(4)
93.18(4)
Scheme 2
triphenylphosphine solubilized copper acetate (Scheme 2), orange
crystals of [Cu(S{O}CFc)(PPh3)2] 2 are obtained upon layering
with pentane at room temperature. The molecular structure of 2,
Fig. 1, shows a monomeric complex, which consists of a single
trigonal planar copper bound to two triphenylphosphine ligands
and a single ferrocenoylthiolate. Selected bond distances and
angles are given in Table 1.
Fig. 2 The molecular structure of [Cu2(l-Se{O}CFc)2(PPh3)3] 3. Hydro-
gen atoms have been omitted for clarity. Thermal ellipsoids are drawn at
40% probability.
selenium atoms◦all lie in the roughly the same plane (sum of angles
˚
Cu2Se2 = 358.8 , with mean deviation of the plane 0.083 A) with
one ferrocenoyl unit extending above the plane and one below
much like that reported for [Cu2(SeC{O}C6H4CH3-4)2(PPh3)3.14
Temperature control proved to be important when synthesizing
the copper selenolate complexes. When the reaction mixture was
warmed to room temperature and subsequently layered with
diethylether, dark orange crystals of [Cu4(l-Se{O}CFc)4(PPh3)4]
4 were obtained in high yield with no evidence for the formation
of dimeric 3 even if additional PPh3 (3 equivalents) was added.
The X-ray structural determination of complex 4 indicated an
arrangement of four [Cu(Se{O}CFc)(PPh3)] units, as shown in
Fig. 3. The M4 fragments are arranged in a distorted tetrahedral
Fig. 1 The molecular structure of [Cu(S{O}CFc)(PPh3)2] 2. Hydrogen
atoms have been omitted for clarity. Thermal ellipsoids are drawn at 40%
probability.
The corresponding reaction in which one equivalent of the
selenide reagent 1b is reacted with (Ph3P)2CuOAc gives rise to
a very different structure from that observed for 2. Cooling
solutions (Et2O–THF) to −25 ◦C afforded orange crystals of
dimeric [Cu2(l-Se{O}CFc)2(PPh3)3] 3 (Fig. 2). The structure of
3 consists of one tetrahedral copper center and one trigonal
planar copper, each bridged by two ferrocenoylselenolates and the
remaining coordination sites are occupied by triphenylphosphine.
The geometry about the Cu centers leads to shorter Cu–Se
˚
fashion with Cu–Cu distances of 3.2956(6)–4.1454(9) A, which
are considerably longer than the sum of the van der Waals
˚
radii (2.8 A) and those observed for 3. Each copper has a
trigonal planar geometry (sum of bond angles around Cu are
359.9◦) and is bridged by two ferrocenoylselenolate ligands
and is bonded to a terminal triphenylphosphine. The Cu–Se
bond distances are 2.3770(13) and 2.4060(13) for Cu(1)–Se(1)
and Cu(1)–Se(1B), respectively (Table 3), which are in accord
with the Cu–Se bond lengths (trigonal planar Cu atoms) in
[Cu6(l-dppm)4(l3-SePh)4](BF4)2.15a The molecule crystallizes in
˚
distances (2.3962(8) and 2.4140(8) A) at the trigonal Cu(1) atom
˚
than the Cu–Se bond lengths (2.5640(8) and 2.5474(8) A) at
¯
the tetrahedral Cu(2) atom. The distortion results in a Cu2Se2
the tetragonal space group I4 with each [Cu(Se{O}CFc)(PPh3)]
˚
rhombus with a Cu(1) · · · Cu(2) distance of 2.6265(9) A which
moiety crystallographically equivalent.
is shorter than the sum of the van der Waals radii of copper
The addition of 1b to PPh3-solubilized AgOAc at −40 ◦C
results in the gradual lightening of the reaction solution upon
warming to room temperature. A reduction in the volume,
followed by slow diffusion of Et2O led to the formation of red
12
˚
(I) (2.8 A). Similar bonding arrangements are also reported
for other Cu2(SeR)2 (R = 4-CH3C6H4C(O), Ph).13,14 Selected
bond lengths and angles are given in Table 2. The copper and
This journal is
The Royal Society of Chemistry 2008
Dalton Trans., 2008, 5048–5053 | 5049
©

View Article Online
◦
˚
Table 5 Selected bond lengths (A) and angles ( ) for 6
Ag(1)–P(1)
Ag(1)–S(1)
Ag(1)–S(2)
Ag(2)–P(2)
Ag(2)–S(2)
Ag(2)–S(1)ꢀ
Ag(1)–Ag(2)
2.4162(11)
2.5171(10)
2.5364(11)
2.4181(11)
2.5310(11)
2.5245(10)
3.2760(5)
P(1)–Ag(1)–S(1)
P(1)–Ag(1)–S(2)
S(1)–Ag(1)–S(2)
P(2)–Ag(2)–S(1)
126.55(4)
124.03(4)
109.40(3)
123.45(4)
129.10(4)
104.50(3)
P(2)–Ag(2)–S(1)ꢀ
S(1)ꢀ–Ag(1)–S(2)
Fig. 3 The molecular structure of [Cu4(l-Se{O}CFc)4(PPh3)4] 4. Hydro-
gen atoms have been omitted for clarity. The same molecular arrangement
is also observed in 5.
crystals of [Ag4(l-Se{O}CFc)4(PPh3)4] 5. X-Ray analysis indicates
that 5 (Fig. S1, electronic supplementary information, ESI†) is
composed of four equivalent [Ag(Se{O}CFc)(PPh3)] units and is
˚
isomorphous to 4. The Ag–Ag distances (3.3143(1)–4.1765(2) A)
are outside the range for reported Ag–Ag interactions,16 although
the Ag(1) · · · Ag(1A) distance is within the sum of the van der
˚
Waals radii for silver (3.4 A). Each silver atom is trigonal planar
(sum of angles around Ag are 359.9◦) with one Ag–Se bond
Fig. 4 The molecular structure of [Ag4(l-S{O}CFc)4(PPh3)4] 6. Phenyl
rings and hydrogen atoms have been omitted for clarity. Thermal ellipsoids
are drawn at 40% probability.
˚
distance shorter than the other (Ag(1)–Se(1) 2.5862(8) A, Ag(1)–
˚
Se(1A) 2.6260(9) A) (Table 4). This disparity is comparable to that
observed in 4 and other trigonal planar silver chalcogenolates
reported,15b,17 and the Ag–Se distances are in a typical range
observed for l2-selenolate ligands between silver atoms.17
the recently reported cluster {Ag[N(Ph2PTe)2]}2.18 There are no
˚
significant Ag–Ag interactions (3.2760(5)–4.3113(13) A observed
The addition of 1a to PPh3-solubilized AgOAc at −40 ◦C
results in the gradual lightening of the reaction solution as it
is warmed to RT. From this solution, orange-red crystals of
[Ag4(l-S{O}CFc)4(PPh3)4] 6 (Fig. 4) could be obtained upon
slow diffusion of diethylether and single crystal X-ray analysis
confirmed that the reaction of 1a with AgOAc also resulted in the
formation of a tetrameric complex. The molecule crystallizes in
in 6), and each silver center exhibits a trigonal planar geometry
(sum of bond angles around Ag 359.9◦) bound to two bridging
ferrocenoylthiolates and one triphenylphosphine ligand. The Ag–
˚
S bond distances range from 2.5171(10)–2.5364(11) A, which is
in accord with other l2-thiolate ligands between silver atoms.19
As seen in Fig. 4, the ferrocenoylthiolate ligands are arranged
together with the PPh3 ligands about a Ag4S4 ring. The Ag4S4 chair
conformation observed in 6 contrasts with the twist boat M4Se4
frameworks observed in 4 and 5.20 Due to the sensitivity of the
FcC(O)TeSiMe3 reagent 1c, analogous tellurolate complexes have
yet to be successfully isolated using these methods.
¯
the space group P1 with a molecule of chloroform and resides
about a crystallographic inversion center, with the two halves
of the molecule equivalent. Selected bond lengths and angles
for 6 are summarized in Table 5. Unlike in 5, 6 contains a
central 8-membered Ag4S4 ring, similar to that observed for
Cyclic voltammetric measurements on dilute solutions of 2–
6 were performed in CH2Cl2 with [NBu4][BF4] (0.1 M) as the
supporting electrolyte. A typical voltammogram of 4 is illustrated
in Fig. 5. Complex 4 undergoes a single irreversible oxidation
at 669 mV followed by two quasi-reversible oxidations at E1/2
of 903 and 1041 mV, respectively (Table 6). Complexes 2–6 all
display similar voltammograms to those observed for 4 with
slightly differing E◦ and E1/2 values. The potentials for these
compounds are given in Table 6. After several cycles, a black
solid was observed precipitating out of solution. Work up and
isolation of the products following bulk electrolysis of a solution of
3 (698 mV) gave FcC(O)Se(O)CFc. The product was confirmed by
comparison with reported 1H NMR spectra.21 We have previously
described a similar observation with ferrocenyl chalcogenolate
clusters in which an initial irreversible oxidation results in cluster
decomposition.8
◦
˚
Table 3 Selected bond lengths (A) and angles ( ) for 4
Cu(1)–Se(1)
Cu(1)–Se(1B)
Cu(1)–P(1)
C(11)–O(1)
2.3770(13)
2.4060(13)
2.226(3)
Se(1)–Cu(1)–Se(1B)
Se(1)–Cu(1)–P(1)
Se(1)ꢀ–Cu(1)–P(1)
110.82(5)
129.05(8)
120.07(8)
1.249(10)
◦
˚
Table 4 Selected bond lengths (A) and angles ( ) for 5
Ag(1)–P(1)
2.439(2)
2.5862(8)
2.6260(9)
3.3143(9)
1.211(8)
1.947(7)
1.453(10)
P(1)–Ag(1)–Se(1)
P(1)–Ag(1)–Se(1)ꢀ
Se(1)–Ag(1)–Se(1)ꢀ
Ag(1)–Se(1)–Ag(1)ꢀ
128.08(6)
116.65(6)
115.12(3)
78.97(2)
Ag(1)–Se(1)
Ag(1)–Se(1A)
Ag(1)–Ag(1A)ꢀ
C(11)–O(1)
C(11)–Se(1)
C(1)–C(11)
5050 | Dalton Trans., 2008, 5048–5053
This journal is
The Royal Society of Chemistry 2008
©

View Article Online
Table 7 Molar absorption coefficients, e, at the corresponding wave-
length, k, of complexes 2–6
Complex
k/nm (e/L mol−1 cm−1
)
[Cu(S{O}CFc)(PPh3)2] 2
351 (4300); 462 (1200)
344 (3300); 464 (860)
349 (24000); 464 (8200)
339 (24000); 455 (7200)
351 (6900); 454 (2600)
[Cu2(l-Se{O}CFc)2(PPh3)3] 3
[Cu4(l-Se{O}CFc)4(PPh3)4] 4
[Ag4(l-Se{O}CFc)4(PPh3)4] 5
[Ag4(l-S{O}CFc)(PPh3)4] 6
Single crystal X-ray diffraction measurements were performed
on an Enraf-Nonius KappaCCD X-ray diffractometer in a cold
nitrogen stream at 150 K (data for 5 were collected at room
temperature) using graphite-monochromated Mo-Ka radiation
Fig. 5 Cyclic voltammogram of a 0.5 mM solution of 4 in CH2Cl2 with
0.1 M [NBu4][BF4] at a scan rate of 100 mV s−1. The peak potentials are
referenced to SCE. Arrows indicate direction of scan.
˚
(k = 0.71073 A) with u and x scans. Data reduction was performed
using Nonius HKL DENZO and SCALEPACK software.27
Molecular structures were determined via direct methods and
Patterson (SHELXS-97) and refined by a full matrix least squares
method based on F2 using SHELXTL 5.0 software.28 Except as
mentioned below, all non-hydrogen atoms were refined anisotrop-
ically. Hydrogen atoms were calculated geometrically and were
riding on their respective atoms. In complex 4 there was two site
disorder of two of the phenyl rings bonded to P(1) and in complex
5 a similar two site disorder was observed for one of the phenyl
rings bound to P(1). The molecules were best refined isotropically
with 50 : 50 occupancy with mild restraints. Crystals of complex
5 were weakly diffracting. Crystallographic data and parameters
are summarized in Table 8.
Table 6 Oxidation potentials of clusters 2–6 in CH2Cl2
Complex
E◦/mV
E1/2 1/mV
E1/2 2/mV
2
3
4
5
6
614
698
669
718
519
838
732
903
477
572
—
872
1041
773
667
The UV-Vis absorption spectra of solutions of complexes 2–
6 all show very similar absorption profiles with two character-
istic maxima in the range 455–464 and 339–349 nm (Table 7).
Each shows a slight red shift relative to the absorptions of
free ferrocene.22 There is an additional band observed for all
complexes at ∼270 nm which may be attributed to metal–ligand
charge transfer (MLCT) transitions.23 The molar absorptivities
for ferrocene based transitions in 2–6 complexes are considerably
greater than those observed for free ferrocene22 but are similar to
other reported ferrocenoyl complexes.24
A BAS 100 electrochemical workstation using a 3-electrode
system, with gold working electrode, platinum flag counter elec-
trode, and a silver wire reference electrode with 0.1 M NBu4BF4 in
CH2Cl2 as the supporting electrolyte was used for electrochemical
measurements. The potentials are reported versus SCE and were
referenced internally to ferrocene (0.528 V), added at the end of the
experiments. UV-Vis absorption measurements were performed on
a Varian Cary Bio 50 spectrometer in CH2Cl2.
Synthesis of FcC(O)SSiMe3 (1a)
LiSSiMe3 (1.90 mmol) in 5 mL of Et2O was added dropwise to a
solution of FcC(O)Cl (1.29 mmol) in 10 mL of Et2O at 0 ◦C and the
reaction was stirred overnight. The resulting cloudy red solution
was filtered over dried Celite and the solvent was removed in vacuo
to yield 1a as a red oil (0.32 g, 80%). NMR data (400 MHz, CDCl3,
23 ◦C) dH 4.95 (2H, m, CH), 4.51 (2H, m, CH), 4.16 (5H, s, Cp),
0.48 (9H, s, SiMe3). dC 217.5 (1C, s, C(O)), 83.9 (1C, s, C), 72.5
(2C, s, CH), 70.9 (5C, s, Cp), 70.9 (2C, s, CH), 0.5 (3C, s, SiMe3).
m/z 321 (M+, 1.9%), 320 (10.9), 319 (23.6), 318 (100), 317 (1.3),
316 (6.3). Anal. Calc. for C14H18FeOSSi: [M+] 318.019709; Found:
[M+] 318.019493.
Experimental
All syntheses were performed under an inert atmosphere using
standard Schlenk-line techniques or a nitrogen-filled glovebox
unless otherwise stated. Solvents tetrahydrofuran, diethyl ether,
hexanes, and pentane purchased from Caledon (HPLC Grade)
were dried by passing through packed columns of activated
alumina using commercially available MBraun MB-SP Series
solvent purification system. Dichloromethane and chloroform,
purchased from Caledon, were distilled over P2O5. Starting
reagents E(SiMe3)2,10 FcC(O)OH,25 FcC(O)Cl,9 LiESiMe3,10 (E =
S, Se, Te) CuOAc,26 were prepared and purified according to
literature preparations. AgOAc and PPh3 were purchased from
Strem Chemicals and Aldrich Chemicals, respectively.
Synthesis of FcC(O)SeSiMe3 (1b)
1
1
1
1H, 13C{ H}, 31P{ H}, 77Se{ H} NMR spectra were obtained on
a Varian INOVA 400 MHz spectrometer at operating frequencies
of 399.763, 100.522, 161.96, 161.83 MHz, respectively, and are
LiSeSiMe3 (2.89 mmol) in 9 mL of Et2O was added dropwise to a
solution of FcC(O)Cl (2.50 mmol) in 15 mL of Et2O at 0 ◦C and
the reaction stirred overnight. The resulting cloudy red solution
was filtered through dried Celite and the solvent subsequently
removed in vacuo to yield a dark red oil, 1b (0.64 g, 75%). NMR
data (CDCl3, 23 ◦C) dH 4.97 (2H, m, CH), 4.57 (2H, m, CH), 4.16
(5H, s, Cp), 0.53 (9H, s, SiMe3). dC 225.2 (1C, s, C(O)), 88.9 (1C, s,
reported in ppm. 1H, 13C{ H}, NMR spectra were referenced
1
internally to residual H and C atoms, respectively, of the deuterated
solvent relative to TMS at 0 ppm. Elemental analyses were
performed by Guelph Chemical Laboratories (Guelph, Canada).
This journal is
The Royal Society of Chemistry 2008
Dalton Trans., 2008, 5048–5053 | 5051
©

View Article Online
Table 8 Selected crystal data, data collection, and refinement parameters for complexes 2–6
2
3
4
5
6
Formula
C47H39CuFeO-
P2S
833.17
Triclinic
¯
P1
9.7676(3)
11.2468(3)
19.1313(5)
75.811(1)
88.090(1)
71.848(1)
1934.02(9)
2
C76H63Cu2Fe2O2-
P3Se2·3(C4H10O)
1720.23
Triclinic
¯
P1
14.7283(6)
16.8262(5)
17.1464(6)
105.192(2)
103.360(2)
91.768(2)
3970.8(3)
2
C116H96Cu4Fe4O4-
P4Se4
2471.21
Tetragonal
¯
I4
C116H96Ag4Fe4O4-
P4Se4
2648.53
Tetragonal
¯
I4
C116H96Ag4Fe4O4-
P4S4·2(CH2Cl2)
2630.78
Triclinic
¯
P1
13.8164(3)
14.4554(3)
15.5570(3)
94.993(3)
114.451(3)
106.023(3)
2645.6(9)
1
Formula weight
Crystal system
Space group
˚
a/A
18.1709(11)
18.5033(8)
˚
b/A
˚
c/A
15.2964(10)
15.5266(8)
a/◦
b/◦
c /◦
3
˚
V/A
5050.6(5)
2
1.625
5315.9(4)
2
1.655
Z
D
calc/g cm−1
1.431
1.098
1.439
1.915
1.651
1.551
l/mm−1
2.942
2.732
F(000)
860
39708
12318(0.0595)
0.0578
0.1549
1768
39245
18212(0.1695)
0.0653
0.1621
2480
2624
1324
47730
13690(0.0733)
0.0548
0.1299
Reflections collected
Independent reflections (Rint
R1 (I > 2r(I))
25354
5817(0.1306)
0.0657
0.1141
150
27163
5560(0.1057)
0.0397
0.0707
296
)
wR2 (I > 2r(I))
Collection temperature/K
150
150
150
C), 73.1 (2C, s, CH), 71.4 (5C, s, Cp), 71.3 (2C, s, CH), 0.7 (3C, s,
SiMe3). m/z 371 (M+, 0.2%), 370 (1.1), 369 (4.7), 368 (22.9), 367
(22.5), 366 (100), 365 (12.8), 364 (56.6), 363 (19.5), 362 (21.3), 361
(1.6), 360 (2.9). Anal. Calc. for C14H18FeOSeSi: [M+] 365.96412.
Found: [M+] 365.96587.
solution was stirred for 1.5 h at 0 ◦C then stored at 3 ◦C overnight.
Et2O was then slowly diffused at RT and the layered reaction was
stored at −25 ◦C. After several days, orange crystals of 3 were
obtained (0.38 g, 86%). NMR data (CDCl3, 23 ◦C) dH 7.42 (18H,
m, CH), 7.29 (18H, m, CH), 7.20 (9H, m, CH), 4.69 (4H, br singlet,
CH), 4.22 (4H, br singlet, CH), 4.01 (10H, s, Cp). kmax/nm 344 (e =
3300) and 464(e = 860). Anal. Calc. (%) for C76H63Cu2Fe2O2P3Se2:
C 60.94 H 4.24. Found: C 62.11, H 4.15.
Synthesis of FcC(O)TeSiMe3 (1c)
LiTeSiMe3 (0.896 mmol) in 3mL of Et2O was added dropwise to a
solution of FcC(O)Cl (0.725 mmol) in 5 mL of Et2O at −40 ◦C and
the reaction stirred overnight protected from light. The resulting
cloudy brown-orange solution was filtered through dried Celite
and the solvent subsequently removed in vacuo to yield a brown
oil (0.19 g, 65%). NMR data (CDCl3, 23 ◦C) dH 4.96 (2H, m, CH),
4.68 (2H, m, CH), 4.19 (5H, s, Cp), 0.62 (9H, s, SiMe3). dC 221.2
(1C, s, C(O)), 98.2 (1C, s, C), 73.9 (2C, s, CH), 72.1 (5C, s, Cp),
70.9 (2C, s, CH), 1.3 (3C, s, SiMe3).
Synthesis of [Cu4(Se{O}CFc)4(PPh3)4] (4)
CuOAc (0.685 mmol) was dissolved in 5 mL of THF with PPh3
(1.370 mmol) and cooled to 0 ◦C. FcC(O)SeSiMe3 (0.685 mmol)
in 5 mL of THF at 0 ◦C was then added dropwise. The dark
orange solution was warmed slowly to room temperature and
stirred overnight. The volume was reduced under vacuum to ∼ 3–
5 mL. Slow diffusion of Et2O gave orange crystals of 4 (0.35 g,
81%). NMR data (CDCl3, 23 ◦C) dH 7.46 (24H, m, CH), 7.28
(24H, m, CH), 7.20 (12H, m, CH), 4.70 (8H, br singlet, CH), 4.23
(8H, br singlet, CH), 4.03 (20H, s, Cp). kmax/nm 354 (e = 24000)
and 448 (e = 8200). Anal. Calc. (%) for C116H96Cu4Fe4O4P4Se4: C
56.38, H 3.92. Found: C 56.36, H 4.16.
Synthesis of [Cu(S{O}CFc)(PPh3)2] (2)
CuOAc (0.529 mmol) was dissolved in 5 mL of THF with PPh3
(1.159 mmol) and cooled to 0 ◦C. FcC(O)SSiMe3 (0.579 mmol) in
5 mL of THF at 0 ◦C was then added dropwise with stirring. The
orange solution was warmed slowly to RT and stirred overnight.
The volume was reduced and the solution was layered with pentane
to yield red-orange crystals of 2 (0.35 g, 85%). NMR data (CDCl3,
Synthesis of [Ag4(Se{O}CFc)4(PPh3)4] (5)
◦
AgOAc (0.605 mmol) and 2 equiv of PPh3 (1.21 mmol) in 5 mL of
THF were cooled to ∼ −40 ◦C and FcC(O)SeSiMe3 (0.605 mmol)
in 5 mL of THF at −40 ◦C was added dropwise. The dark orange
solution was stirred for ∼ 1.5 hrs at −40 ◦C then warmed slowly
to 0 ◦C. The reaction was stored at −4 ◦C for 15 hrs. The volume
was reduced to ∼ 3–5 mL and layered with Et2O to afford red
crystals of 6 (0.34 g, 87%). NMR data (CDCl3, 23 ◦C) dH 7.38
(24H, m, CH), 7.29 (24H, m, CH), 7.20 (12H, m, CH), 4.71 (8H, s,
CH), 4.24 (8H, s, CH), 4.11 (20H, s, Cp). kmax/nm 339 (e = 24000)
and 455 (e = 7200). Anal. Calc. (%) for C116H96Ag4Fe4O4P4Se4: C
52.60, H 3.65. Found: C 52.35, H 3.39.
23 C) dH 7.41 (12H, m, CH), 7.30 (12H, m, CH), 7.22 (6H, m,
CH), 4.79 (2H, br singlet, CH), 4.24 (2H, br singlet, CH), 4.05
(5H, s, Cp). kmax/nm 351 (e = 4300) and 462 (e = 1200). Anal.
Calc. (%) for C47H39CuFeOPS: C 67.75, H 4.72. Found: found C
67.38, H 5.02.
Synthesis of [Cu2(Se{O}CFc)2(PPh3)3] (3)
CuOAc (0.754 mmol) was dissolved in 5 mL of THF with PPh3
(1.508 mmol) and cooled to 0 ◦C. FcC(O)SeSiMe3 (0.754 mmol)
in 5 mL THF was then added dropwise with stirring. The orange
5052 | Dalton Trans., 2008, 5048–5053
This journal is
The Royal Society of Chemistry 2008
©

View Article Online
Trans., 2003, 515; (b) R. D. Adams and B. Qu, J. Organomet. Chem.,
2001, 620, 303; (c) G.-L. Zheng, J.-F. Ma, Z.-M. Su, L.-K. Yan, J.
Yang, Y.-Y. Li and J.-F. Liu, Angew. Chem., Int. Ed., 2004, 43, 2409;
(d) V. Chandrasekhar, S. Nagendran, S. Bansal, M. A. Kozee and D. R.
Powell, Angew. Chem., Int. Ed., 2000, 39, 1833; (e) C. Nitschke, A. I.
Wallbank, D. Fenske and J. F. Corrigan, J. Cluster Sci., 2007, 18, 131.
7 (a) V. N. Soloviev, A. Eichho¨fer, D. Fenske and U. Banin, J. Am. Chem.
Soc., 2000, 122, 2673; (b) V. N. Soloviev, A. Eichho¨fer, D. Fenske and
U. Banin, J. Am. Chem. Soc., 2001, 123, 2354.
8 (a) T. P. Lebold, D. L. B. Stringle, M. S. Workentin and J. F. Corrigan,
Chem. Commun., 2003, 1398; (b) A. I. Wallbank, A. Borecki, N. J.
Taylor and J. F. Corrigan, Organometallics, 2005, 24, 788; (c) A. I.
Wallbank and J. F. Corrigan, Chem. Commun., 2001, 377; (d) C.
Nitschke, D. Fenske and J. F. Corrigan, Inorg. Chem., 2006, 45, 9394.
9 A. Aguilar-Aguilar, A. D. Allen, E. P. Cabrera, A. Fedorov, N. Fu, H.
Henry-Riyad, J. Leuninger, U. Schmid, T. T. Tidwell and R. Verma,
J. Org. Chem., 2005, 70, 9556.
Synthesis of [Ag4(S{O}CFc)4(PPh3)4] (6)
AgOAc (0.551 mmol) was dissolved in 5 mL of THF with
PPh3 (1.10 mmol) and the colorless solution was cooled to
−40 ◦C. FcC(O)SSiMe3 (0.551 mmol) in 5 mL of THF at −40 ◦C
was added dropwise. The reaction was warmed to RT and stirred
over night. The THF was removed and the solid was dissolved in
10 mL of CH2Cl2. Slow diffusion of Et2O gave orange crystals of
5 (0.28 g, 85%). NMR data (CDCl3, 23 ◦C) dH 7.46 (24H, m, CH),
7.34 (24H, m, CH), 7.30 (12H, m, CH), 4.81 (8H, m, CH), 4.25
(8H, m, CH), 4.14 (20H, s, Cp). kmax/nm 351 (e = 6900) and 454
(e = 2600). Anal. Calc. (%) for C116H96Ag4Fe4O4P4S4: C 56.61, H
3.93. Found: C 56.30, H 3.62.
10 D. Taher, A. I. Wallbank, E. A. Turner, H. L. Cuthbert and J. F.
Corrigan, Eur. J. Inorg. Chem., 2006, 4616.
11 J. Ku¨hnert, M. Lamacˇ, T. Ru¨ffer, B. Walfort, P. Steˇpnicˇka and H. Lang,
Conclusions
ˇ
In summary, multiple ferrocenoyl ligated copper(I) and silver(I)
chalcogenolate cluster complexes can be conveniently prepared
using the new ferrocenoyl chalcogenide reagents FcC(O)ESiMe3.
Although, incorporating a carbonyl moiety between the fer-
rocene and chalcogen has been shown to spatially remove two
ferrocene units from one another,21 it does not prevent cluster
decomposition upon oxidation of clusters 2–6.
J. Organomet. Chem., 2007, 692, 4303.
12 A. Bondi, J. Phys. Chem., 1964, 68, 441.
13 J. Kampf, R. Kumar and J. P. Oliver, Inorg. Chem., 1992, 31, 3626.
14 Z. Lu, W. Huang and J. J. Vittal, New J. Chem., 2002, 26, 1122.
15 (a) V. W.-W. Yam, C.-H. Lam, W. K.-M. Fung and K.-K. Cheung,
Inorg. Chem., 2001, 40, 3435; (b) V. W.-W. Yam, E. C.-C. Cheng and N.
Zhu, New J. Chem., 2002, 26, 279.
16 M. C. Gimeno and A. Laguna, Comprehensive Coordination Chemistry
II, ed. J. A. McCleverty and T. B. Meyer, Elsevier Pergamon, Oxford,
2004, vol. 6, ch. 6.7.
17 D. Fenske and T. Langetepe, Angew. Chem., Int. Ed., 2002, 41,
Acknowledgements
300.
18 M. C. Copsey, A. Panneerselvam, M. Afzaal, T. Chivers and P. O’Brien,
Dalton Trans., 2007, 1528.
We gratefully acknowledge the Natural Sciences and Engineer-
ing Research Council (NSERC) of Canada for funding. The
University of Western Ontario and the Canada Foundation for
Innovation are thanked for equipment funding.
19 E. Barreiro, J. S. Casas, M. D. Couce, A. Sanchez, R. Seoane, J. Sordo,
J. M. Varela and E. M. Vazquez-Lopez, Dalton Trans., 2007, 3074.
20 J. Pe´rez, L. Garc´ıa, M. Kessler, K. Nolsøe, E. Pe´rez, J. L. Serrano, J. F.
Mart´ınez and R. Carrascosa, Inorg. Chim. Acta, 2005, 358, 2432.
21 S. Kumar, S. K. Tripathi, H. B. Singh and G. Wolmersha¨user,
J. Organomet. Chem., 2004, 689, 3046.
22 (a) Y. S. Sohn, D. N. Hedrickson and H. B. Gray, J. Am. Chem. Soc.,
1971, 93, 3603; (b) A. T. Armstrong, A. T. Smith, E. Elder and S. P.
McGlynn, J. Chem. Phys., 1967, 46, 4321.
23 G. Li, Y. Song, H. Hou, L. Li, Y. Fan, Y. Zhu, X. Meng and L. Mi,
Inorg. Chem., 2003, 42, 913.
24 W. C. du Plessis, T. G. Vosloo and J. C. Swarts, J. Chem. Soc., Dalton
Trans., 1998, 2507.
25 B. Breit and D. Breuninger, Synthesis, 2005, 16, 2782.
26 D. A. Edwards and R. J. Richards, J. Chem. Soc., Dalton Trans., 1973,
2436.
27 Z. Otwinowski and W. Minor, HKL DENZO and SCALEPACK v
1.96, Processing of X-ray Diffraction Data Collected in Oscillation
Mode.
References
1 Ferrocenes: Homogeneous Catalysis, Organic Synthesis, ed. A. Togni
and T. Hayashi, Materials Science VHC, Weinheim, 1994.
2 (a) A. Lebande, J. Ruiz and D. Astruc, J. Am. Chem. Soc., 2002, 124,
1782; (b) M. C. Daniel, J. R. Aranzaes, S. Nlate and D. Astruc, J. Inorg.
Organomet. Polym., 2005, 15, 107; (c) M. Li, P. Cai, C. Duan, F. Lu,
J. Xie and Q. Meng, Inorg. Chem., 2004, 43, 5174; (d) O. A. Jimenez,
S. Chikneyan, A. J. Baca, J. Wang and F. Zhou, Environ. Sci. Technol.,
2005, 39, 1209.
3 P. Nguyen, P. G. Elipe and I. Manners, Chem. Rev., 1999, 99, 1515.
4 S. Nakashima, S. Nakazaki, H. Sakai, M. Watanabe, I. Motoyama and
M. Sato, Inorg. Chem., 1998, 37, 1959.
5 D. Astruc, M.-C. Daniel and J. Ruiz, Chem. Commun., 2004, 2637.
6 (a) M. Kondon, T. Shinagawa, M. Miyazawa, Md. K. Kabir, Y. Irie,
T. Horiba, T. Naito, K. Maeda, S. Utsuno and F. Uchida, Dalton
28 G. M. Sheldrick, SHEXTL 97-2, Program for the solution of crystal
structures, University of G
o¨ttingen, Germany, 1997.
This journal is
The Royal Society of Chemistry 2008
Dalton Trans., 2008, 5048–5053 | 5053
©