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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
Experimental
General procedures
Benzene-1,2-dithiol
Complex 1-Ph
Complex 2-OH
Complex 3-OCOFc
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
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
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).
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)
Table 3
MeCN
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
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
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
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.
redox event is between the dianion and its parent complex rather
than the dimerisation of the monoanion.
11130 | Dalton Trans., 2012, 41, 1112511133
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
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.
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.