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Three diiron complexes bearing an aromatic ring as mimics of the diiron


subunit of [FeFe]-hydrogenase: synthesis, electron transfer and coupled
chemical reactions
Jia Zhao,a Zhenhong Wei,a Xianghua Zenga and Xiaoming Liu*a,b
Received 19th May 2012, Accepted 13th July 2012
DOI: 10.1039/c2dt31083j

Three diiron complexes (1-Ph, 2-OH, and 3-OCOFc) as mimics of the diiron subunit of [FeFe]hydrogenase were electrochemically investigated in 0.1 mol L1 [NBut4]BF4acetonitrile (MeCN) under
CO and Ar atmosphere. Complex 3-OCOFc was prepared from the reaction of complex 2-OH with
ferrocenylacyl chloride (FcOCCl). The complex was fully characterised using a variety of spectroscopic
techniques. Its structure was established using X-ray single crystal diffraction analysis. In addition to the
well-established ECE (E for electrochemical and C for chemical) mechanism, it was revealed that a
further reversible reduction at a potential more negative by ca. 600 mV was observed under CO
atmosphere. It was further proposed based on the analysis of electrochemical and infrared spectroscopic
data that the second redox was due to a two-electron process of supposedly a tetrairon cluster. This
product was formed in situ from the reaction between the dianion generated from the ECE process and its
parent complex (1-Ph, 2-OH, and 3-OCOFc) and is supposedly of a core Fe4(II). This reaction
occurred only when CO was presented. Under Ar atmosphere, bulk electrolysis led to fully-reduced
products, that is, with the iron at the oxidation state of zero, but complex 2-OH was an exception. An
overall mechanism to describe the electron transfer and coupled chemical reactions under CO atmosphere
was proposed.

Introduction
Due to the relevance of diironcarbonyl complexes to the diiron
subunit of [FeFe]-hydrogenase, investigations into the chemistry
of the diiron complexes of the core {Fe2(CO)x} (x = 46) have
attracted considerable attention since the structural revelation of
the [FeFe]-hydrogenase over a decade ago, Fig. 1 (left).1,2 This
metalloenzyme catalyses both hydrogen evolution and oxidation
and has a strong preference towards the catalysis of proton
reduction.3 In the electrocatalysis of the proton reduction by
either the enzyme or the mimics, electron transfer of the diiron
centre has fundamental importance. In the last decade there have
been numerous diiron complexes reported as models of the
diiron subunit of the enzyme in the literature.410
Electrochemistry of those systems has been one of the main
concerns under investigation. It is well understood that the
electrochemistry of these complexes varies greatly from one

Department of Chemistry, Nanchang University, Nanchang 330031,


China. E-mail: xiaoming.liu@ncu.edu.cn; Tel: +86 (0)573 83643937
b
College of Biological, Chemical Sciences and Engineering, Jiaxing
University, Jiaxing 314001, China. E-mail: xiaoming.liu@mail.zjxu.edu.cn;
Tel: +86 (0)573 83643937
Electronic supplementary information (ESI) available: Further information on electrochemistry and bulk electrolysis. CCDC 876228 for
complex 3-OCOFc. For ESI and crystallographic data in CIF or other
electronic format see DOI: 10.1039/c2dt31083j

This journal is The Royal Society of Chemistry 2012

Fig. 1 Schematic view of the H-cluster of the [FeFe]-hydrogenase


(left) and three complexes bearing aromatic ring moiety (right, Fc =
ferrocenyl group).

another and so do their catalytic behaviours. Although the


medium in which the electrochemistry is conducted has an
important role to play, intrinsically, the bridging linkage of the
diiron centre and the additional substituents of the organic skeleton have profound inuence on the electron transfer. It has been
established that diiron complexes of the core, {Fe2(CO)x} (x =
46), adopt an ECE mechanism with potential inversion. It
means that the second reduction potential may be more positive
than the rst one.1113 In this mechanism, a chemical reaction
(C1) follows the rst electron transfer before the second electron
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transfer occurs. Further chemical reaction(s) (C2) may also


follow the second electron transfer. The chemical reaction C2
decides the reversibility of the reduction of the diiron centre. The
chemical reaction C1 usually involves isomerisation which gives
an intermediate to accept the second electron. But C1 could be
accompanied with parallel chemical reaction(s) (C1) which
would lead to falling apart of the diiron moiety before proceeding to the second electron transfer. This accounts for why
the electron number of the reduction of the diiron centre is generally between 1 and 2.13 Introducing a bidentate thiolate rather
than two identical thiolates can signicantly suppress both the
chemical reactions C1 and C1.9 Indeed, when the bridging
linkage of strong electron-withdrawing property is presented,
such as o-carborane (1,2-closo-C2B10H12), 2,2-biphenyl and
1,8-naphthalene, relevant complexes showed two successive
one-electron reductions.1416 When the bidentate thiolates bear
such a moiety, for instance, an aromatic system, then the electron
density can substantially be diverted away from the dimetallic
centre upon reduction and the reversibility of the reduction of
the diiron centre can be signicantly improved.
The rst example of such a diiron complex was derived from
1,2-benzenedithiolate; complex 1-Ph, Fig. 1 (right). This
complex was rst reported in the early 1980s.17 The complex
had been re-investigated as a mimic of the diiron subunit of the
[FeFe]-hydrogenase and that it produced molecular hydrogen
electrocatalytically with the presence of acetic acid.1820 Because
of the conjugating effect of the aromatic system which can
buffer the electron density of the metal centre, the redox reactions of the catalyst are modulated by lowering the potential
difference between successive reductions.19
While attention was focused on the ECE mechanism and
related catalysis of proton reduction, we noticed that a reversible
reduction process was observed in addition to the rst two-electron reduction under CO atmosphere. This process involves CObinding. It is undoubtable that a wider vision of the electrochemistry would have relevance to fully understand the catalysis
of the complexes. To this end, we further looked into this
coupled chemical reaction(s) using cyclic voltammetry, bulk
electrolysis, chemical reduction, and infrared spectroscopy of the
three complexes, Fig. 1 (right), of which complex 3-OCOFc is
rst reported. Herein, we report its synthesis, characterisation,
and electrochemical investigation in comparison with the other
two complexes. A mechanism to describe the electron transfers
and their coupled chemical reactions of the three complexes was
also proposed.

Experimental
General procedures

All organic solvents were pre-treated and freshly distilled under


Ar atmosphere prior to use. Electrochemistry was performed in a
gas-tighten three-electrode system in which a vitreous carbon
disk ( = 1 mm) was used as a working electrode, a carbon strip
as counter electrode, and Ag/AgCl (inner reference solution:
0.45 mol L1 [NBut4]BF4 + 0.05 mol L1 [NBut4]Cl in dichloromethane) against which the potential of ferrocenium/ferrocene
couple is 0.55 V in 0.5 mol L1 [NBut4]BF4 in dichloromethane.
Further details for electrochemical experimental details can be
11126 | Dalton Trans., 2012, 41, 1112511133

found elsewhere.13,21,22 All potentials reported in this work were


quoted against ferrocenium/ferrocene couple.
Bulk electrolysis was performed in a self-designed miniH-type cell. The volume of working solution was usually 23 mL.
A platinum mesh ( = 1 cm, h = 2 cm) was used as working
electrode and a carbon strip (ca. 5 mm 40 mm) as the counter
electrode. All the bulk electrolysis was performed by holding the
potential at 1.5 V.
Materials and synthesis

Ferrocenecarboxaldehyde and oxalyl chloride in analytical grade


were purchased from Aladdin (Shanghai, China) and used as
received. Triethylamine was purchased from Sinopharm Chemical Reagent Co. Ltd and was puried by distillation with sodium
prior to use. Precursor [Fe2(-S)2(CO)6] was prepared following
a literature procedure.23 So were complexes 1-Ph, 2-OH and
ferrocenylcarbonyl chloride (FcCOCl).20

Benzene-1,2-dithiol

A stirred solution of tetramethylethylenediamine (3.3 mL,


21.9 mmol) and n-BuLi (17 mL, 49.8 mmol) in hexanes
(20 mL) was cooled to ice temperature in an ice bath. To the suspension was slowly added thiophenol (2 mL, 19.6 mmol). The
reaction mixture was kept at 0 C for 1 h and then stirred overnight at room temperature. The solution was precooled to
20 C before the addition of S8 (0.7 g, 21.9 mmol). After stirring for 2 h, the reaction mixture was warmed to room temperature and stirred further overnight. The reaction mixture was
acidied by adding 5% HCl (40 mL, 20 mmol) and then was
extracted with ether (30 mL 3). The organic phases were combined and dried with MgSO4 before the solvents were removed
under reduced pressure. Purication using column chromatography (hexanes) produced the desired compound as a paleyellow solid (1.3 g, 45%).

Ferrocenyl formyl chloride (FcOCCl)

To the solution of ferrocenyl carboxylic acid FcCOOH (5 g,


21 mmol) in CH2Cl2 (30 mL) under 0 C was dropwise added a
solution of oxalyl dichloride (ClCOCOCl) (8 mL, 50 mmol) in
CH2Cl2 (50 mL). The mixture was stirred for 8 h at room temperature under argon atmosphere. Removal of the solvent produced a crude product. Further washing the crude product with
hexanes gave the product as a red solid (3.4 g, 65%). IR (KBr)
vCO: 1765 cm1. The complex was used for next reaction
without further purication.

Complex 1-Ph

Fe3(CO)12 (1.45 g, 2.88 mmol) and benzene-1,2-dithiol (0.41 g,


2.88 mmol) were dissolved in toluene (20 mL). The mixture was
reuxed for 1.5 h under argon atmosphere before the removal of
the solvent under reduced pressure. Purication by column
chromatography yielded complex 1-Ph as red powder (685 mg,
57%). 1H NMR (600 MHz, CDCl3): = 6.64 (d, 2H, C6H2),
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7.14 (m, 2H, C6H2). IR (MeCN): v(CO): 2080, 2044,


2004 cm1.

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Complex 2-OH

[Fe2(-S)2(CO)6] (100 mg, 0.29 mmol) and 1,4-benzoquinone


(95 mg, 0.88 mmol) were dissolved in anhydrous THF (100 mL)
under anaerobic condition and then transferred into a photoreactor (KPL-LAM500). The reaction was irradiated for about
5 min at room temperature ( = 254 nm). Removal of the solvent
accrued a residue which was puried using ash chromatography
on silica gel (ethyl acetatepetroleum ether = 1 : 5) to give the
product. Crystallisation of the product by layering its solution in
dichloromethane with hexanes produced dark-red plate-shaped
crystals (23.0 mg, 18%). In either dichloromethane or toluene,
the complex was prepared in similar yield. 1H NMR (600 MHz,
CDCl3): = 6.21 (d, 2H, C6H2). IR(CH2Cl2): v(CO), 2074,
2038, 1998 cm1.

can adopt two conformations, syn-1 and syn-2, Scheme 1. Proton


NMR in the region for the ferrocenyl proton suggested only one
type of ferrocenyl group existed in solution. Although in its solid
state, the complex adopted the syn-2 form, syn-1 is more likely
in solution. The conformation in the solid state may result from
packing effects.
The crystallographic details of complex 3-OCOFc are tabulated in Table 1 and its structure is shown in Fig. 2. As shown in
the structure, the entire arrangement of the diiron centre, the two
ferrocenyl groups, and the phenyl ring compose a balance-like
conguration. Overall, the diiron-carbonyl core of the complex
is structurally analogous to other diiron hexacarbonyl complexes
reported (Table 2).9,13,20

Complex 3-OCOFc

To a solution of complex 2-OH (0.1 g, 0.22 mol) and NEt3


(0.1 mL, 1 mmol) in CH2Cl2 (20 mL) was added dropwise a solution of FcCOCl (0.1 g, 0.5 mmol) in CH2Cl2 (10 mL). The
mixture was stirred for 8 h at room temperature under argon
atmosphere. Removal of the solvent produced a red crude
product which was puried by using ash chromatography on
silica gel (eluent: ethyl acetatepetroleum ether = 1 : 4) to give a
red solid (0.14 g, 75%). Microanalysis for complex 3-OCOFc
(C34H20O10S2Fe4, Fw = 875.79): cal. (found), C%, 46.62
(46.50); H% 2.30 (2.47). 1H NMR (600 MHz, CDCl3) 3anti, =
7.194 (s, 2H, C6H2), 4.23424.9150 (9H, Fc), 4.24504.8410
(9H, Fc); 3syn, = 7.194 (s, 2H, C6H2), 4.23424.9150 (18H,
Fc). IR (MeCN): v(CO), 2083.4, 2048.7, 2009.0 cm1, vCvO,
1735 cm1.

Scheme 1 Synthesis of complex 3-OCOFc ( please note that the conformations of the two isomers for complex 3-OCOFc are illustrative
only).

Table 1

Results and discussion


Synthesis and structural analysis

The ligand, benzene-1,2-dithiol, used to prepare complex 1-Ph


was synthesised following a literature procedure via reaction of
benzenethiol and S8.24 FcOCCl was synthesised from the reaction of oxalyl dichloride with ferrocenyl carboxylic acid.25 Reaction of the dithiolate with triiron dodecacarbonyl produced
complex 1-Ph.20 Complex 2-OH was prepared by reacting
[Fe2(-S)2(CO)6] with 1,4-benzoquinone under irradiation.26
3-OCOFc was prepared through the reaction of complex 2-OH
with ferrocenyl formyl chloride in good yield using an analogous procedure we reported recently.13 Despite the conformation
of the two ferrocenyl groups in the solid state (vide infra) in
which the two groups are at the same side proximal to the
{Fe2(CO)6} unit, proton resonance NMR did reveal two conformations in solution. Analogous to the diiron hexacarbonyl complexes which possess two identical thiolates bridging the two
iron atoms,9,13,27,28 the orientations of the two ferrocenyl groups
against the diiron-carbonyl motif give three isomers, anti, syn-1,
and syn-2. While the rst form is unambiguous, the syn-form
This journal is The Royal Society of Chemistry 2012

Crystallographic data of complex 3-OCOFc

Empirical formula
Formula weight
Temperature
Wavelength
Crystal system, space group
Unit cell dimensions
Volume
Z, Calculated density
Absorption coefcient
F(000)
Crystal size
Theta range for data collection
Limiting indices
Reections collected/unique
Completeness to = 28.30
Absorption correction
Renement method
Data/restraints/parameters
Goodness-of-t on F2
Final R indices
[I > 2(I)]
R indices (all data)
Largest diff. peak and hole

C34H20Fe4O10S2
875.65
296(2) K
0.71073
Monoclinic, P 21/c
a = 11.702(2) , = 90
b = 16.020(3) , = 100.585(2)
c = 20.250(4) , = 90
3731.5(12) 3
2, 1.635 Mg m3
1.762 mm1
1844
0.25 0.24 0.20 mm
2.18 to 28.04
15 h 15, 21 k 21,
26 l 26
34 087/9055 [R(int) = 0.0224]
99.5%
Semi-empirical from equivalents
Full-matrix least-squares on F2
9055/1/463
1.017
R1 = 0.0403, wR2 = 0.1230
R1 = 0.0589, wR2 = 0.1405
0.940 and 0.359 e 3

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Fig. 2 Crystal structure of complex 3-OCOFc (ellipsoid thermal probability was drawn at the level of 30% and hydrogen atoms were omitted
for clarity).

Table 2 Selected bond lengths () and angles () of complex


3-OCOFc
Fe(2)Fe(4)
Fe(2)S(1)
Fe(2)S(2)
Fe(4)S(1)
Fe(4)S(2)
Fe(2)C(4)
Fe(2)C(5)
Fe(2)C(6)
Fe(4)C(1)
Fe(4)C(2)
Fe(4)C(3)
Fe(2)S(1)Fe(4)
Fe(4)S(2)Fe(2)
S(1)Fe(2)S(2)
S(2)Fe(4)S(1)
S(1)Fe(2)Fe(4)
S(2)Fe(2)Fe(4)
S(1)Fe(4)Fe(2)
S(2)Fe(4)Fe(2)

2.4810(8)
2.2539(10)
2.2729(10)
2.2527(7)
2.2636(9)
1.789(4)
1.808(4)
1.804(4)
1.814(6)
1.787(4)
1.784(4)
66.43(3)
66.31(3)
80.97(3)
80.72(3)
57.20(3)
56.67(3)
56.38(3)
57.03(3)

Electrochemical behaviours of complexes 1-Ph, 2-OH, and


3-OCOFc

The electrochemistry of the three complexes in acetonitrile is


shown in Fig. 3. The rst reduction processes of complexes 1-Ph
and 2-OH were in agreement with those reported by Lichtenberger, Evans and Glass.18,19,29,30 As seen in Fig. 3, complex
3-OCOFc exhibited essentially the same reduction process as
those of the other two despite the attachment of two ferrocenyl
groups. All the reduction potentials are tabulated in Table 3. In
general, the assignment of the rst reduction to the process of
{Fe(I)Fe(I)}/{Fe(0)Fe(0)} following an ECE mechanism is
unambiguous.5,6,10,13 In the anodic region, both complex 1-Ph
and 2-OH showed similar metal-based oxidation processes, and
the height of the oxidation peaks may suggest a multi-electron
process. In the oxidation of complex 3-OCOFc, the oxidation
process of the incorporated ferrocenyl groups came before the
oxidation of its diiron core. Due to the oxidation of the ferrocenyl groups, the oxidation potential of the diiron core of complex
3-OCOFc is driven positively compared to the other two complexes (Fig. S1, in which only the oxidation process of the ferrocenyl groups is shown). Due to their electron-withdrawing
nature, the oxidation of the incorporated ferrocenyl groups
became more difcult at about 300 mV (Fig. S1). To estimate
11128 | Dalton Trans., 2012, 41, 1112511133

Fig. 3 Cyclic voltammograms of complexes (a) 1-Ph, (b) 2-OH, and


(c) 3-OCOFc (3 mmol L1) in 0.1 mol L1 [NBut4]BF4/MeCN under
Ar atmosphere (dotted line) and CO atmosphere (solid line) at various
ranges of scanning potentials (scanning rate = 0.1 V s1, 298 K).

Table 3
MeCN

Redox potentials of complexes 1-Ph, 2-OH, and 3-OCOFc in


1

1.35
1.34
1.28
1.36
1.34
1.28

1.28
1.21
1.23
1.27
1.25
1.22

1.31
1.275
1.26
1.31
1.29
1.25

1.95
1.79
1.89

Epc

1-Ph
2-OHa
3-OCOFca
1-Phb
2-OHb
3-OCOFcb
a

Epa

Ep1/2

Epc

1.86
1.71
1.81

1.91
1.75
1.85

Epa

Ep1/2

Under CO atmosphere. b Under Ar atmosphere.

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the electron numbers involved in the rst reduction of the complexes, the ratio of the peak height of the reduction over that of
the oxidation of the ferrocene intramolecularly incorporated
(complex 3-OCOFc) was calculated. That the peak height of the
incorporated ferrocenyl groups in 3-OCOFc is approximately
equal to the peak height of its rst reduction in either CO or Ar
atmosphere further supported the assignment of a two-electron
process. At the scanning rates of 0.1 V s1, the electron numbers
derived from the calibration for the reduction of 3-OCOFc are
1.7 and 2.1 under CO and Ar atmosphere, respectively. By lowering the scanning rate to 0.01 V s1, the calibrated electron
numbers under the two working atmospheres are 1.2 and 1.9,
respectively. The calibrated electron number at varying scanning
rate is shown in Fig. S2. The trend shown in Fig. S2 implies
that the monoanion from the rst electron transfer undergoes
another chemical reaction (C1 in Scheme 2) in addition to the
coupled reaction whose product accepts the second electron
transfer. Apparently, this reaction ought to be slower compared
to the reaction in the ECE process since the rst stage appeared
at an extremely low scanning rate.
Further examination of the electrochemistry of those complexes revealed an additional reversible redox process after the
rst one when the atmosphere is switched to CO. The second
redox process occurs at a potential approximately 600 mV more
negative than that of the rst one (Fig. 3 and Table 3), although
the second process is only observable with the presence of CO.
The sensitivity of the second process to CO atmosphere rules out
the possibility that it is the further reduction of the dianion from
the rst process. In other words, the second process originated
from the product of a chemical reaction associated with the rst
redox process. It has been reported that reducing diiron carbonyl
complexes led to formation of tetrairon clusters via dimerisation
of the monoanion generated from the one-electron reduction of
its parent complex.15,3133 But as shown in Table 4, the coupled
chemical reaction in the ECE process is still signicant even at
the scanning rate of 0.01 V s1. The coupled reaction is so fast

Scheme 2 The proposed mechanism for the electron transfer and


coupled chemical reactions of the three diiron complexes under CO.
Please note that redox E3 is supposedly an ECE process with potential
inversion.

Table 4 Electron number estimated from bulk electrolysis under CO


and Ar atmosphere (298 K), respectively
Complex

1-Ph

2-OH

3-OCOFc

nCO
nAr

0.99 0.04
1.8 0.2

1.05 0.06
1.48 0.07

0.98 0.06
1.57 0.01

This journal is The Royal Society of Chemistry 2012

that the monoanion may not have the time to undergo such a
dimerisation. By considering the electrophilicity of the starting
complexes (complexes of this kind readily undergo substitution
reaction by nucleophiles) and that the dianion may possess a
decoordinated thiolate,12 one possibility is that the dianion may
react with its parent complex to form a tetrairon cluster.
Although either pathway leads to a tetrairon cluster of a core
with the same oxidation states, that is, oxidation state of 0.5 on
average, the chemistry involved is fundamentally different.
Therefore, it would be interesting to elucidate what happened
after the rst redox event.

The formation of the possible tetrairon cluster and its reduction

To gain further information for the relation of the rst redox


process to the second reduction, bulk electrolysis at 1.5 V was
carried out under CO and Ar, respectively. The products gave
rather clean electrochemical responses after the electrolysis
(Fig. S3 and S4). As it has been known that, overall, the rst
process involves two electrons due to the ECE mechanism. But
the charge consumed during the electrolysis under CO atmosphere was only half the charge calculated based on the ECE
mechanism of two-electron, that is, equivalent to one electron
per molecule for all the three complexes, Tables 4 and S1. This
is in agreement with the above hypothesis that the dianion may
undergo reaction with the precursor. The charge consumed
during the electrolysis suggested strongly that the reaction proceeded at a 1 : 1 ratio to produce a tetranuclear product responsible for the second reduction process. As shown in Tables 4 and
S1, switching the working atmosphere from CO to Ar brought
the estimated electron number via bulk electrolysis close to 2,
but still less than 2. The reasons for the observations are, (i) the
reaction occurs only with the presence of CO as discussed earlier
and (ii) the coupled chemical reaction C1 which occurred at low
scanning rate (Fig. S2) would disfavour the ECE mechanism.
All the experimental results suggest that the product, possibly a
tetrairon cluster, has a mixed oxidation state of {Fe(I)Fe(I)Fe(0)
Fe(0)}, that is, oxidation state of 0.5 on average. Compared to
the precursor, the oxidation number of each diiron unit changed
from 2+ to 1+ on average.
One might argue that same conclusion would be drawn from
the bulk electrolysis if the formation of the tetrairon resulted
from the dimerisation of the monoanion. If such a dimerisation
does exist, it must be part of the reaction C1, a reaction coupled
to the rst electron transfer in parallel with the other coupled
reaction C1, Scheme 2. But the results from varying the scanning
rate (Fig. 4) suggested that compared to reaction C1, reaction(s)
C1 is much slower since slightly raising the scanning rate from
0.01 to 0.1 V s1 noticeably suppressed the reaction C1. This is
particularly signicant for complex 3-OCOFc. For this complex,
the electron number involved in the rst process was rather close
to 2 at a scanning rate of 0.01 V s1 even under the atmosphere
of CO (vide ante). Therefore, in addition to the viewpoint of
electrophilicity of the parent complex and the nucleophilicity of
the dianion generated from the rst reduction as discussed previously, the results derived from varying the scanning rate are
further supportive of our argument that the reaction after the rst
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Fig. 4 Cyclic voltammograms of complexes (a) 1-Ph, (b) 2-OH, and


(c) 3-OCOFc (3 mmol L1) in 0.1 mol L1 [NBut4]BF4CH3CN under
CO atmosphere (298 K) at various scanning rates. Please note that 2
equivalents of ferrocene were added into the solutions of the rst two
complexes to calibrate the electron number.

redox event is between the dianion and its parent complex rather
than the dimerisation of the monoanion.
11130 | Dalton Trans., 2012, 41, 1112511133

The cyclic voltammograms at various scanning rates revealed


some further information about the reaction between the dianion
and its parent complex and the electrochemistry of the second
redox process, Fig. 4. Among the three complexes, the ease of
the formation of the tetrairon clusters follows the trend, 2-OH <
1-Ph < 3-OCOFc. As its electrochemical response at 0.01 V s1
under CO atmosphere suggested, the last complex may have the
most complete reaction involving its dianion. At this scanning
rate, the electron number involved in the rst reduction process
is rather close to 2 as discussed earlier. The observation that the
peak heights of the two reductions at scanning rate of 0.01 V s1
are approximately the same may imply that the reduction of the
formed tetrairon clusters is also a two-electron process
(Fig. S5). This is further supported by the ratio (ca. 2) of the
oxidation peak current of the incorporated ferrocenyl groups
(4 for each tetrairon unit) over that of the reduction peak
current of the cluster after bulk electrolysis (Fig. S3). It is
interesting to note that this further implies that the tetrairon
cluster may similarly undergo an ECE process with potential
inversion for the single-waved reduction like its parent diiron
complex. Perhaps for multinuclear iron complexes/clusters in
which the iron atoms are bridged together by multidentate
ligands, their electron transfer feasibly follows such an ECE
mechanism with potential inversion. In addition to the diiron
complexes of a {Fe(I)Fe(I)} core and the tetrairon clusters discussed in this work, we recently, indeed, found that diiron complexes of a {Fe(II)Fe(II)} core adopt this mechanism in their
electron transfer.8
Attempt to isolate the products was not successful via both
electrochemical and chemical means, which made it impossible
to establish the absolute identities of those products. Nevertheless, their infrared spectra were measured immediately after the
electrolysis, Fig. 5. For straightforward comparison, the peak
positions of those bands are tabulated in Table 5. As shown in
Fig. 5, the products generated from the three parent complexes
exhibited clean spectra with a similar spectral pattern. Thus, it
could be concluded in the light of both electrochemical (Table 3)
and spectral data (Fig. 4 and Table 5) that these tetrairon clusters
are structurally analogous. Furthermore, compared to the absorption bands of their parent complexes (1-Ph, 2-OH, and
3-OCOFc), those clusters generated from the reaction of the
dianion with its parent complex underwent red shift by ca.
60 cm1 on average. This shift falls right in the range of
variations in infrared spectral absorption when the oxidation
state of a system, either the diiron21,34 or tetrairon one,35 undergoes a change by one unit. This is in agreement with the variation in oxidation state for the diiron unit as proposed above.
There have been reports that upon reduction, diiron hexacarbonyl
complexes formed tetrairon clusters and the bridging carbonyl
was very often involved.15,3133 But in this investigation, no
bridging CO was observed as indicated by their infrared spectra
(Fig. 5). Although, no explanation could be offered for why
these products showed no bridging carbonyl, their infrared
absorption bands are, in general, comparable with those of the
tetrairon clusters reported in the literature, Fig. 6.15,32,33 These
comparable infrared spectral data suggest that the iron core of
the products which exhibit a quasi-reversible redox process
has the same oxidation state as those reported, that is, probably
{Fe(I)Fe(I)Fe(0)Fe(0)}.
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Table 5 Comparison of the infrared spectra before and after the bulk
electrolysis under CO atmosphere
Complex

Precursor, CO (cm1)

Product, CO (cm1)

1-Ph
2-OH
3-OCOFc

2080, 2044, 2004


2078, 2041, 2001
2083, 2048, 2008, 1735a

2011, 1996, 1927


2020, 1994, 1936
2016, 1994, 1934, 1727a

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Assigned to the ester group linking to the ferrocenyl group.

Fig. 6 Comparison of the infrared absorption bands of the parent complexes (black rhombus, the tetrairon clusters and red circle and blue
square for the product formed initially). 4 = [Fe2(-bpdt)(CO)6] (bpdt =
biphenyl-2,2-dithiolate),15 5 = [Fe2(-edt)(CO)6] (edt = 1,2-ethanedithiolate),32 6 = [Fe2(-pdt)(CO)6] ( pdt = 1,3-propanedithiolate),33 7 =
[Fe2(-padmt)(CO)6] ( padmt = ( phenylazanediyl)dimethanethiolate).33

Fig. 5 IR spectra of the precursors (solid line) and their products generated from bulk electrolysis at 1.5 V (dashed line) in 0.1 mol L1
[NBut4]BF4MeCN under CO atmosphere (298 K) (a) 1-Ph, (b) 2-OH,
and (c) 3-OCOFc.

As shown in Table 4 and Fig. 5, working atmosphere severely


affected the reduction product. Except for complex 2-OH, the
bulk electrolysis of the other two complexes gave absorption
This journal is The Royal Society of Chemistry 2012

bands at much lower frequencies under Ar. Recently, Tilley and


co-workers investigated chemically the reduction of complex
1-Ph by using sodium as reducing agent and successfully isolated
its product.36 It turned out that the product is a fully reduced
tetrairon with a {4Fe(0)} core stabilised by four sodium ions.
Compared to the parent complex, the major absorption bands
shifted towards lower frequency by about 130 cm1, which is
comparable with those of the products generated in bulk electrolysis of complexes 1-Ph and 3-OCOFc under Ar and approximately one-folder larger than the infrared spectral shifts between
the parent complexes and the products generated from bulk electrolysis under CO (vide ante). These shifts are, respectively, in
agreement with their changes in oxidation state after the
reduction. It is obvious that the reduction of both complexes
1-Ph and 3-OCOFc under Ar produced two-electron-reduced
products via either chemical or electrochemical reductions. The
observations prompted us to examine how the reduction proceeds under CO when sodium is used as reducing agent. The
reduction product of complex 1-Ph reduced by sodium under
CO turned out no difference from that obtained under Ar
(Fig. S6). This can probably be attributed to the strong reducing
capability of sodium.
The electron transfers and coupled chemical reactions of the
three diiron complexes under CO are depicted in Scheme 2. It
has to be pointed out that additional reactions may be coupled to
the species, {Fe2PhR2}, {Fe2PhR2}, and {Fe2PhR2}2 but
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these reactions may not be dominant and were omitted for simplicity in the scheme. It is also worth mentioning the electrochemical reversibility of the three diiron complexes, particularly
under Ar atmosphere. Since E2 is more positive than E1, oxidation of {Fe2PhR2}2 at the potential of 1Epc (Table 3) is not
possible. There must be coupled chemical reaction(s) to convert
it into a form which is more vulnerable for oxidation. Fast scanning did reveal that the oxidation potential 1Epa shifted positively, Table 3 and Fig. 4. This is because the shifted potential
contains the contribution from the potential at which the species,
{Fe2PhR2}2, is possibly oxidised before the isomerisation reaction which brings the oxidation potential down to a more negative value.
Bulk electrolysis under Ar did not lead to a neat two-electron
reduction (Table 4). Among the three complexes, complex 1-Ph
showed a nearly perfect two-electron process (1.8e) whereas the
other two complexes gave a deviation by ca. 25%. These observations are supportive of the existence of the coupled chemical
reaction (C1, Scheme 2) after the input of the rst electron. It is
noteworthy that for both complexes 1-Ph and 3-OCOFc, the
huge red shift in the infrared spectra of the products suggested
their full reduction from Fe(I) to Fe(0), Fig. 6a and 6c. But for
complex 2-OH, the reduction gave a reasonably stable product
and did not proceed that far in terms of the electron number
involved based on the infrared spectrum (Fig. 5b). Its unusual
behavior may be associated with the reactivity of the two
hydroxyl groups on the phenyl ring.

Conclusions
In summary, the electrochemistry and the coupled chemical reactions of three complexes, 1-Ph, 2-OH, and 3-OCOFc were
reported. Unlike the other two, 3-OCOFc had not been reported
before and bore an aromatic ring on which was further functionalised symmetrically with two ferrocenyl groups. The incorporated ferrocenyl groups were employed to calibrate the electron
numbers involved in the reduction of the complex. The complex
was fully characterised including using crystallographic analysis
to establish its identity. Alongside with the other two analogous
complexes, 1-Ph and 2-OH, the complex was electrochemically
investigated to disclose the mechanisms of electron transfer and
coupled reactions. The same methodology we reported recently
was used to conrm the ECE mechanism of diironcarbonyl
complexes.13
These diiron complexes exhibited one more quasi-reversible
redox process at a potential more negative by ca. 600 mV under
CO atmosphere. Our electrochemical investigations suggest that
the product responsible for the second redox process was generated from the reaction between the dianion from the rst
reduction and its parent complex. The daughter product is likely
a tetrairon cluster with 0.5 oxidation number on average for each
iron atom. Experimental observations showed that the singlewaved quasi-reversible redox process is a two-electron process
analogously following the ECE mechanism with potential inversion as found for its parent complex.
The results obtained from this investigation and our recent
ndings for diiron complexes with a core of {Fe(II) Fe(II)}8
suggest that the ECE mechanism with potential inversion
11132 | Dalton Trans., 2012, 41, 1112511133

commonly exists in the electron transfer of complexes of multiiron centres despite the oxidation state. It is also clear that the
substituent on the aromatic ring, or the bridging linkage of the
diiron complexes, exerted signicant inuence not only on the
coupled chemical reaction(s) (C1, Scheme 2), but also the reaction of the dianion with its parent complex. The functional
group, OH, of the complex 2-OH probably alters the entire
electron transfer process.

Acknowledgements
We thank the Natural Science Foundation of China (Grant Nos.
20871064 and 21171073), Ministry of Science and Technology
(China) (973 program, Grant No. 2009CB220009), and the
Government of Zhejiang Province (Qianjiang Professorship for
XL) for supporting this work.

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