Polyhedron 149 (2018) 1–6

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Polyhedron
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Diiron ethanedithiolate complexes with pendant ferrocene: Synthesis,

characterization and electrochemistry
Dan-Ting Lu a, Jiao He b, Xiao-Yong Yu a, Xu-Feng Liu a,⇑, Yu-Long Li b,⇑, Zhong-Qing Jiang c
a
School of Materials and Chemical Engineering, Ningbo University of Technology, Ningbo 315211, China
b
College of Chemistry and Environmental Engineering, Sichuan University of Science & Engineering, Zigong 643000, China
c
Department of Physics, Key Laboratory of ATMMT Ministry of Education, Zhejiang Sci-Tech University, Hangzhou 310018, China

a r t i c l e i n f o a b s t r a c t

Article history: Three diiron ethanedithiolate complexes containing pendant ferrocene were prepared and structurally
Received 7 February 2018 characterized. Reaction of the complex [{l-SCH2CH(CH2OH)S}Fe2(CO)6] (1) with ferrocenecarboxylic acid
Accepted 10 April 2018 in the presence of N,N0 -dicyclohexylcarbodiimide and 4-dimethylaminopyridine afforded complex
Available online 21 April 2018
[{l-SCH2CH(CH2O2CFc)S}Fe2(CO)6] (Fc = ferrocenyl) (2) in 73% yield. Further treatment of complex 2 with
a monophosphine ligand tris(2-methoxyphenyl)phosphine or tris(2-furyl)phosphine in the presence
Keywords: of the decarbonylating agent Me3NO2H2O yielded the monophosphine-substituted complexes
Diiron ethanedithiolate
[{l-SCH2CH(CH2O2CFc)S}Fe2(CO)5P(2-C6H4OCH3)3] (3) and [{l-SCH2CH(CH2O2CFc)S}Fe2(CO)5P(2-C4H3O)3]
Ferrocene
Monophosphine
(4) in 94% and 85% yields, respectively. The complexes 2–4 were characterized by elemental analysis,
X-ray crystallography spectroscopy and X-ray crystallography. In addition, electrochemical properties of the complexes 2–4
Electrochemistry were studied by cyclic voltammetry.
Ó 2018 Elsevier Ltd. All rights reserved.

1. Introduction monophosphine [28], diphosphine [29], cyanide [30], N-hetero-

Hydrogenases are a class of natural enzyme that can catalyze
the reversible conversion of protons into hydrogen in microorgan-
isms [1–5]. According to the metal atoms in the active site,
hydrogenases can be classified into [NiFe]-hydrogenases, [FeFe]-
hydrogenases and [Fe]-hydrogenases [6–11]. Among these hydro-
genases, [FeFe]-hydrogenases are the most efficient with respect
to others in the reduction of proton [7]. Consequently, since the
discovery of the active site of [FeFe]-hydrogenases, research on
the biomimic chemistry of the [FeFe]-hydrogenases has been
received more and more attention during the past decades [12–17].
X-ray crystallographic studies revealed that the active site of
[FeFe]-hydrogenases, as shown in Fig. 1 (A), consists of a butterfly
diiron dithiolate cluster coordinated by carbonyls, cyanides and a
cysteinyl ligand [18,19]. The bridging dithiolate was previously
suggested as propanedithiolate [20–22] or azadithiolate [23–25].
Diiron propanedithiolate complex [(l-SCH2CH2CH2S)Fe2(CO)6]
(Fig. 1, B) [26] and diiron azadithiolate complex [(l-SCH2NRCH2-
S)Fe2(CO)6] (Fig. 1, C) [27] were successfully made by chemists to
mimic the active site of [FeFe]-hydrogenases. Moreover, further
reactions of the complex B or C with other ligands, for example,
⇑ Corresponding authors.
E-mail addresses: nkxfliu@126.com (X.-F. Liu), yu_longli@aliyun.com (Y.-L. Li).
cyclic carbene [31], gave the corresponding derivatives in recent
years.
The diiron ethanedithiolate complex [{l-SCH2CH(CH2OH)S}]
Fe2(CO)6] (Figs. 1, 1) was prepared by the heating reaction of
Fe3(CO)12 with the dithiol 2,3-dimercapto-1-propanol in 2001
[32]. However, further reactions of complex 1 with acid are still
rare in the literature. We [33,34] and others [35,36] reported some
diiron dithiolate complexes with intermolecular bridging 1,10 -bis
(diphenylphosphino)ferrocene, intramolecular bridging 1,10 -bis
(diphenylphosphino)ferrocene or monosubstituted diphenylphos-
phinoferrocene. Recently, we are interested in the esterification
of complex 1 with ferrocenecarboxylic acid as well as further reac-
tions of complex 2 with a monophosphine ligand. We choose phos-
phine ligands as the substitute for the cyanide found in the active
site of [FeFe]-hydrogenases because the phosphine ligands are
easily available and the phosphine-containing diiron complexes
are much more stable than cyanide-containing complexes. As a
result, three diiron complexes containing ferrocene were success-
fully prepared and structurally characterized. In this paper, we
describe the synthesis, spectroscopy, X-ray crystallography and
electrochemistry of the diiron ethanedithiolate complexes contain-
ing pendant ferrocene related to the active site of [FeFe]-
hydrogenases.

https://doi.org/10.1016/j.poly.2018.04.015
0277-5387/Ó 2018 Elsevier Ltd. All rights reserved.
2 D.-T. Lu et al. / Polyhedron 149 (2018) 1–6
Fig. 1. The active site of [FeFe]-hydrogenases (A) and synthetic model complexes B,
C and 1.
2. Experimental
2.1. Materials and methods
Ferrocenecarboxylic acid, N,N0 -dicyclohexylcarbodiimide (DCC),
4-dimethylaminopyridine (DMAP), tris(2-methoxyphenyl)phos-
phine, tris(2-furyl)phosphine and Me3NO2H2O were available
commercially and used as received. Complex 1 [32] was prepared
according to literature procedures. IR spectra were recorded on a
Nicolet MAGNA 560 FTIR spectrometer. NMR spectra were
obtained on a Bruker 500 MHz spectrometer. Elemental analyses
were performed by a Perkin-Elmer 240C analyzer. UV–Vis spectra
were obtained on a Hitachi U-4100 spectrometer.
2.2. Synthesis of [{l-SCH2CH(CH2O2CFc)S}Fe2(CO)6] (2)
To a solution of [{l-SCH2CH(CH2OH)S}Fe2(CO)6] (0.201 g, 0.5
mmol), 4-dimethylaminopyridine (0.024 g, 0.2 mmol) and fer-
rocenecarboxylic acid (0.138 g, 0.6 mmol) in CH2Cl2 (10 mL) was
added N,N0 -dicyclohexylcarbodiimide (0.124 g, 0.6 mmol). The
mixture was stirred at room temperature for 12 h and then the sol-
vent was reduced on a rotary evaporator. The residue was sub-
jected to TLC separation using CH2Cl2/petroleum ether = 2:3 (v/v)
as eluent. From the main yellow band, 0.225 g (73%) of complex
2 was obtained as a red solid. IR (CH2Cl2, cm1): mC„O 2077 (s),
2037 (vs), 2004 (vs), 1996 (vs); mC@O 1717 (m). 1H NMR (500
MHz, CDCl3): 4.84 (t, J = 1.75 Hz, 2H, C5H4), 4.44 (t, J = 1.75 Hz,
2H, C5H4), 4.23 (s, 5H, C5H5), 4.16 (dd, J = 7.2, 11.2 Hz, 1H, OCH2),
4.03 (dd, J = 8.2, 11.7 Hz, 1H, OCH2), 3.04 (quint, J = 7 Hz, 1H,
SCH), 2.73 (dd, J = 7.7, 13.2 Hz, 1H, SCH2), 1.96 (dd, J = 5.5, 13.5
Hz, 1H, SCH2) ppm. 13C{1H} NMR (125 MHz, CDCl3): 208.13
(C„O), 171.27 (C@O), 71.73, 70.32, 70.03 (C5H4), 69.91 (C5H5),
65.58 (OCH2), 52.27 (SCH), 39.09 (SCH2) ppm. Anal. Calc for C20H14-
Fe3O8S2: C, 39.12; H, 2.30. Found: C, 38.89; H, 2.44%. UV–Vis (kmax,
nm; e, M1cm1 in CH2Cl2): 325 (15449).
2.3. Synthesis of [{l-SCH2CH(CH2O2CFc)S}Fe2(CO)5P(2-C6H4OCH3)3]
(3)
To a solution of 2 (0.062 g, 0.1 mmol) and tris(2-methoxyphe-
nyl)phosphine (0.035 g, 0.1 mmol) in CH2Cl2 (5 mL) was added a
solution of Me3NO2H2O (0.011 g, 0.1 mmol) in MeCN (2 mL). The
mixture was stirred at room temperature for 1 h and then the sol-
vent was reduced on a rotary evaporator. The residue was sub-
jected to TLC separation using CH2Cl2/petroleum ether = 1:1 (v/v)
as eluent. From the main red band, 0.088 g (94%) of complex 3
was obtained as a red solid. IR (CH2Cl2, cm1): mC„O 2041 (vs),
1983 (vs), 1937 (m); mC@O 1713 (m). 1H NMR (500 MHz, CDCl3):
7.40 (s, 4H, PhH), 6.95, 6.85 (2s, 8H, PhH), 4.77, 4.71 (2s, 2H,
C5H4), 4.40 (s, 2H, C5H4), 4.16 (s, 5H, C5H5), 3.86 (dd, J = 8, 11 Hz,
1H, OCH2), 3.77 (dd, J = 7.5, 11 Hz, 1H, OCH2), 3.55 (s, 9H, 3CH3),
1.54 (s, 2H, SCH2), 1.43 (s, 1H, SCH) ppm. 31P{1H} NMR (200 MHz,
CDCl3, 85% H3PO4): 49.53 (s) ppm. 13C{1H} NMR (125 MHz, CDCl3):
215.87 (d, JP-C = 8.5 Hz, PFeC„O), 215.55 (d, JP-C = 8.5 Hz, PFeC„O),
210.66 (C„O), 170.95 (C@O), 160.23, 131.82, 119.73, 111.13 (PhC),
71.33, 70.70, 70.14 (C5H4), 69.83 (C5H5), 66.20 (OCH2), 54.72 (CH3),
49.81 (SCH), 37.72 (SCH2) ppm. Anal. Calc for C40H35Fe3O10PS2: C,
51.20; H, 3.76. Found: C, 51.33; H, 3.83%. UV–Vis (kmax, nm; e,
M1 cm1 in CH2Cl2): 370 (10480).
2.4. Synthesis of [{l-SCH2CH(CH2O2CFc)S}Fe2(CO)5P(2-C4H3O)3] (4)
The procedure was similar to that of 3 except tris(2-furyl)phos-
phine (0.023 g, 0.1 mmol) was used instead of tris(2-methoxyphe-
nyl)phosphine; 0.070 g (85%) of complex 4 was obtained as a red
solid. IR (CH2Cl2, cm1): mC„O 2052 (vs), 1994 (vs); mC@O 1713
(m). 1H NMR (500 MHz, CDCl3): 7.73 (s, 3H, furylH), 6.94–6.93
(m, 3H, furylH), 6.50–6.49 (m, 3H, furylH), 4.78 (d, J = 1.5 Hz, 2H,
C5H4), 4.42 (t, J = 2 Hz, 2H, C5H4), 4.20, 4.18 (2s, 5H, C5H5), 4.03–
3.94 (m, 2H, OCH2), 2.54–2.47 (m, 1H, SCH2), 2.11–2.08 (m, 1H,
SCH2), 1.67 (dd, J = 5.7, 11.2 Hz, 1H, SCH) ppm. 31P{1H} NMR
(200 MHz, CDCl3, 85% H3PO4): 11.93 (s) ppm. 13C{1H} NMR (125
MHz, CDCl3): 212.98 (d, JP-C = 4.5 Hz, PFeC„O), 212.91 (d, JP-C =
4.5 Hz, PFeC„O), 209.79 (C„O), 171.05 (C@O), 148.28 (d, JP-C =
5.1 Hz, 5-furylC), 147.37 (d, JP-C = 67.5 Hz, 2-furylC), 121.49 (d,
JP-C = 17.4 Hz, 3-furylC), 111.36 (d, JP-C = 6.9 Hz, 4-furylC), 71.50,
70.49, 70.19 (C5H4), 69.85 (C5H5), 66.05 (OCH2), 50.68 (d, JP-C =
4.2 Hz, SCH), 38.37 (SCH2) ppm. Anal. Calc for C31H23Fe3O10PS2: C,
45.51; H, 2.83. Found: C, 45.58; H, 3.12%. UV–Vis (kmax, nm; e,
M1 cm1 in CH2Cl2): 351 (10640).
2.5. X-ray structure determination
Single crystals of 2–4 suitable for X-ray diffraction analysis
were grown by slow evaporation of CH2Cl2/hexane solutions at 4
°C. A single crystal of 2–4 was mounted on a Bruker D8 QUEST
CCD diffractometer. Data were collected at 296 K using a graphite
monochromator with Mo Ka radiation (k = 0.71073 Å) in the x-/
scanning mode. Data collection and reduction were used by APEX2
[37]. Absorption correction was performed by SADABS program [38].
Using OLEX2 [39], the structure was solved by direct methods
using the SHELXS-97 program [40] and refined by full-matrix least-
squares techniques SHELXL-97 [40] on F2. Hydrogen atoms were
located using the geometric method. Details of crystal data, data
collections and structure refinement are summarized in Table 1.
2.6. Electrochemical experiment
Electrochemical properties of the complexes 2–4 were studied
by cyclic voltammetry (CV) in CH2Cl2 solution. Electrochemical
measurements were carried out under nitrogen using a CHI 620
Electrochemical work station. As the electrolyte, n-Bu4NPF6 was
recrystallized multiple times from a CH2Cl2 solution by the addi-
tion of hexane. CV scans were obtained in a three-electrode cell
with a glassy carbon electrode (3 mm diameter) as the working
electrode, a platinum wire as the counter electrode, and a non-
aqueous Ag/Ag+ electrode as the reference electrode. The potential
 D.-T. Lu et al. / Polyhedron 149 (2018) 1–6 3

Table 1
Crystal data and structure refinements details for 2–4.

Complex 2 3 4
Empirical formula C20H13Fe3O8S2 C40H35Fe3O10PS2 C31H23Fe3O10PS2
Formula weight 612.97 938.32 818.13
T (K) 296(2) 296(2) 296(2)
Crystal system monoclinic monoclinic triclinic
Space group C2/c P21/n P1
a (Å) 32.5396(17) 12.6853(5) 10.3606(5)
b (Å) 7.7348(4) 17.9307(7) 10.6473(4)
c (Å) 23.6783(13) 17.6610(7) 17.4596(8)
a (°) 90 90 91.4350(10)
b (°) 126.8570(10) 97.3400(10) 94.6380(10)
c (°) 90 90 118.8860(10)
V (Å3) 4768.4(4) 3984.2(3) 1676.32(13)
Z 8 4 2
Dcalc (g cm3) 1.708 1.564 1.621
l (mm1) 2.019 1.280 1.508
F(0 0 0) 2456.0 1920.0 828.0
Crystal size (mm) 0.34  0.22  0.14 0.16  0.14  0.12 0.32  0.22  0.16
Radiation Mo Ka (k = 0.71073) Mo Ka (k = 0.71073) Mo Ka (k = 0.71073)
2h range (°) 5.494–55.114 4.544–50.828 4.38–50.788
hkl range 42  h  42 15  h  15 12  h  12
9  k  10 21  k  21 12  k  12
30  l  30 21  l  21 21  l  21
Reflections collected 59 532 74 595 53 895
Independent reflections 5465 [Rint = 0.0439] 7347 [Rint = 0.0386] 6133 [Rint = 0.0340]
Data/restraints/parameters 5465/1/298 7347/0/508 6133/0/424
Goodness of fit (GOF) on F2 1.077 1.082 1.093
Final R indexes (I > 2r(I)) 0.0684/0.1542 0.0443/0.1221 0.0493/0.1517
Final R indexes (all data) 0.0957/0.1684 0.0621/0.1436 0.0579/0.1674
Largest difference in peak and hole (e Å3) 0.47/0.39 1.45/0.73 1.32/0.85

scale was calibrated against the Fc/Fc+ couple and reported versus (for 2) and d 3.86, 3.77 ppm (for 3) for the hydrogens of the methy-
this reference system. lene group attached to the ester group, whereas the 1H NMR spec-
trum of complex 4 displays a multiplet in the region of d 4.03–3.94
ppm for the hydrogens of the methylene group attached to the
3. Results and discussion ester group. The 31P{1H} NMR spectra of the complexes 3 and 4
exhibit a singlet at d 49.53 and 11.93 ppm, respectively, in good
3.1. Synthesis and characterization of the complexes 2–4 agreement with phosphine-substituted diiron complexes [45–47].
The 13C{1H} NMR spectrum of complex 2 demonstrates a singlet
The synthetic route is depicted in Scheme 1. Treatment of com- at d 208.13 ppm for the terminal carbonyls. In contrast, the 13C
plex 1 with 1.2 equivalents of ferrocenecarboxylic acid in the pres- {1H} NMR spectra of the complexes 3 and 4 demonstrate two
ence of the dehydrating agent N,N0 -dicyclohexylcarbodiimide and
the catalyst 4-dimethylaminopyridine afforded complex 2 with
pendant ferrocene in 73% yield. Further treatment of complex 2
with a monophosphine ligand tris(2-methoxyphenyl)phosphine
or tris(2-furyl)phosphine in the presence of Me3NO2H2O gave
the monophosphine-substituted complexes 3 and 4 with pendant
ferrocene in 94% and 85% yields, respectively. The complexes 2–4
are air and moisture stable red solids, which have been character-
ized by elemental analysis and spectroscopy. The IR spectrum of
complex 2 shows four absorption bands in the region of 2077–
1996 cm1 for the stretching vibrations of the terminal carbonyls,
comparable to the all-carbonyl diiron analogous [41–43]. The lar-
gest mC„O of the IR spectra of the complexes 3 (2041 cm1) and 4
(2052 cm1) are moving towards lower frequency with respect to
that of complex 1 because the monophosphine ligand has stronger
electron-donating than CO [44]. The 1H NMR spectra of the com-
plexes 2 and 3 display two doublet/doublet at d 4.16, 4.03 ppm

Scheme 1. Preparation of complexes 2–4. Fig. 2. ORTEP view of 2 with 30% probability level ellipsoids.
4 D.-T. Lu et al. / Polyhedron 149 (2018) 1–6
Fig. 3. ORTEP view of 3 with 30% probability level ellipsoids.
Fig. 4. The 1-D chain of complex 3.
doublets and a singlet for the terminal carbonyls due to the cou-
pling between phosphorus and carbons. The resonances from 1H,
31 1
P{ H} and 13C{1H} are in accord with the crystal structures of
the complexes 2–4.
3.2. X-ray crystal structures of the complexes 2–4
The structures of the complexes 2–4 were determined by X-ray
crystallography. While the ORTEP and packing views are shown in
Figs. 2–6, the selected bond distances and angles are given in
Table 2. Complex 2 crystallizes in monoclinic space group C2/c
with eight molecules in the unit cell and one molecule in the asym-
metric unit. As shown in Fig. 2, complex 2 features a diiron
ethanedithiolate cluster with six terminal carbonyls and a pendant
ferrocene. The FeAFe bond distance [2.4797(13) Å] is shorter than
Fig. 5. ORTEP view of 4 with 30% probability level ellipsoids.
Fig. 6. The 1-D chain of complex 4.
that of complex 1 [2.4998(6) Å] [48] probably due to the influence
of ferrocene.
Complex 3 crystallizes in monoclinic space group P21/n with
four molecules in the unit cell and one molecule in the asymmetric
unit. As shown in Fig. 3, complex 3 features a diiron ethanedithio-
late cluster with five terminal carbonyls, a monophosphine ligand
tris(2-methoxyphenyl)phosphine and a pendant ferrocene. The
phosphorus atom of tris(2-methoxyphenyl)phosphine occupies
an apical position of the distorted square-pyramidal geometry of
the Fe2 atom, very similar to the monophosphine-substituted
diiron complexes [49–51]. The FeAFe bond distance [2.5220(7) Å]
is longer than that of complex 2 due to the monophosphine ligand
having stronger electron-donating than CO [44], but shorter than
those in natural [FeFe]-hydrogenases [18,19] as well as in some
diphosphine-substituted diiron complexes [52–54]. As compared
to complex 2, the pendant ferrocene in complex 3 is further away
from the diiron unit due to the steric repulsion between ferrocene
and tris(2-methoxyphenyl)phosphine. The distance of Fe2-Fe3 in
complex 3 (8.113 Å) is remarkably longer than that in complex 2
(6.579 Å). As shown in Fig. 4, there is only one kind of C–H  O
hydrogen bond in the 1-D chain of complex 3. The intermolecular
C8B-H  O5A hydrogen bond between the methylene and terminal
carbonyls with the distance of 2.563 Å is observed in the crystal
packing.
Complex 4 crystallizes in triclinic space group P 1  with two
molecules in the unit cell and one molecule in the asymmetric unit.
As shown in Fig. 5, similar to complex 3, complex 4 features a
diiron ethanedithiolate cluster with five terminal carbonyls, an
apically coordinated tris(2-furyl)phosphine and a pendant fer-
rocene. The FeAFe bond distance [2.5190(9) Å] is slightly shorter
 D.-T. Lu et al. / Polyhedron 149 (2018) 1–6 5

Table 2
Selected bond distances (Å) and angles (°) for 2–4.

2
Fe1–Fe2 2.4797(13) Fe1–S1 2.2359(16)
Fe1–S2 2.2383(19) Fe2–S1 2.230(2)
Fe2–S2 2.240(2) C7–C8 1.491(9)
C8–C9 1.219(9) C10–C11 1.436(9)
S1–Fe1–Fe2 56.17(6) S1–Fe1–S2 80.16(6)
S2–Fe1–Fe2 56.41(6) S1–Fe2–Fe1 56.38(5)
S1–Fe2–S2 80.24(7) S2–Fe2–Fe1 56.35(6)
Fe2–S1–Fe1 67.45(5) Fe1–S2–Fe2 67.24(6)
C9–C8–C7 123.3(7) C8–C9–O7 124.3(7)
C10–O7–C9 116.6(7) O7–C10–C11 112.3(5)
3
Fe1–Fe2 2.5220(7) Fe1–S1 2.2456(11)
Fe1–S2 2.2473(11) Fe2–S1 2.2603(11)
Fe2–S2 2.2581(12) Fe2–P1 2.2751(10)
C6–C7 1.488(6) C9–C10 1.482(7)
S1–Fe1–Fe2 56.24(3) S1–Fe1–S2 79.75(4)
S2–Fe1–Fe2 56.16(3) S1–Fe2–Fe1 55.69(3)
S2–Fe2–Fe1 55.76(3) S2–Fe2–S1 79.21(4) Fig. 8. Cyclic voltammogram of 3 (1.0 mM) with HOAc (0, 2, 4, 6, 8, 10 mM) in 0.1 M
P1–Fe2–Fe1 152.77(3) Fe1–S1–Fe2 68.07(3) n-Bu4NPF6/CH2Cl2 at a scan rate of 100 mVs1.
C6–C7–C8 114.7(4) O6–C8–C7 103.3(4)
C9–O6–C8 115.3(4) O6–C9–C10 109.1(4)
4
Fe1–Fe2 2.5190(9) Fe1–S1 2.2524(12)
Fe1–S2 2.2415(13) Fe2–S1 2.2524(11)
Fe2–S2 2.2517(11) Fe2–P1 2.2072(11)
C6–C7 1.513(6) C9–C10 1.464(6)
S1–Fe1–Fe2 56.00(3) S2–Fe1–Fe2 56.09(3)
S2–Fe1–S1 79.84(4) S1–Fe2–Fe1 56.00(3)
S2–Fe2–Fe1 55.71(3) S2–Fe2–S1 79.62(4)
P1–Fe2–Fe1 151.66(4) Fe1–S1–Fe2 68.00(3)
C8–C7–C6 110.0(3) O6–C8–C7 108.0(3)
C9–O6–C8 114.3(3) O6–C9–C10 112.1(3)

Fig. 9. Cyclic voltammogram of 4 (1.0 mM) with HOAc (0, 2, 4, 6, 8, 10 mM) in 0.1 M
n-Bu4NPF6/CH2Cl2 at a scan rate of 100 mVs1.

3.3. Electrochemical properties of the complexes 2–4

The electrochemical properties of 2–4 were studied by cyclic

Fig. 7. Cyclic voltammogram of 2 (1.0 mM) with HOAc (0, 2, 4, 6, 8, 10 mM) in 0.1 M
n-Bu4NPF6/CH2Cl2 at a scan rate of 100 mVs1.
than that of complex 3, but obviously longer than that of complex
2. It is interesting to find out that the orientation of the ferrocene in
complexes 3 and 4 is different. That is, the orientation of the fer-
rocene in complex 3 is in the same direction with the monophos-
phine ligand. However, the orientation of the ferrocene in
complex 4 is in the opposite direction with the monophosphine
ligand. As shown in Fig. 6, there are two C–H  O hydrogen bonds
between the two adjacent molecules in the 1-D chain of complex 4.
Intermolecular C31A-H  O7B and C31B-H  O7A hydrogen bonds
between the furyl and ester carbonyl with the distance of 2.536
Å are observed in the crystal packing.
voltammetry in CH2Cl2 solution. The CV curves of 2 are displayed
in Fig. 7. As shown in Fig. 7, complex 2 displays one quasi-reversi-
ble reduction process at 1.65 V and, which can be ascribed to the
reduction of FeIFeI to FeIFe0. Meanwhile, complex 2 displays one
reversible oxidation process at 0.26 V for the oxidation of FeII to
FeIII. Due to the electron-withdrawing effect of ester group, the oxi-
dation potential is higher than ferrocene. Furthermore, complex 2
is found to have the catalytic ability for proton reduction to H2 in
the presence of HOAc under CV conditions. As shown in Fig. 7,
upon addition of the first 2 mM of HOAc to the solution of 2, the
first reduction peak at 1.65 V was slightly increased, whereas
the second reduction potential of 2, the current peak at 2.06 V
increased markedly with increasing concentration of HOAc, indi-
cating that complex 2 has the ability to catalyze the electrocat-
alytic reduction of proton to H2. Moreover, according to the
above-mentioned electrochemical observations of 2, an EECC (E
= electrochemical; C = chemical) catalytic mechanism can be pro-
posed for the electrocatalytic H2 production of 2 in the presence
of the weak acid HOAc [55–60]. Moreover, the electrochemical
behaviors of 3 and 4 were also examined (Figs. 8 and 9). Complex
6 D.-T. Lu et al. / Polyhedron 149 (2018) 1–6
3 and 4 display one irreversible reduction process at 1.92 V,
1.81 V and one reversible oxidation processes at ca. +0.26 V,
which can be ascribed to the reduction of FeIFeI to FeIFe0 and the
oxidation of FeII to FeIII, respectively. It is noteworthy that the
reduction potentials of 3 and 4 are more negative than those of
2, obviously due to the fact that tris(2-methoxyphenyl)phosphine
and tris(2-furyl)phosphine are stronger electron-donating than
CO ligand. In addition, the results show that complexes 3 and 4
can also be regarded as electrocatalysts for hydrogen production
in the presence of HOAc.
4. Summary
In summary, three diiron ethanedithiolate complexes 2–4 with
pendant ferrocene have been successfully synthesized in very high
yields by esterification or carbonyl substitution. The structures of
the complexes 2–4 were characterized by X-ray crystallography.
The Fe-Fe bond distances of the complexes 3 and 4 are longer than
that of complex 2. The orientation of the ferrocene in complex 3 is
different from that in complex 4. In addition, electrochemical stud-
ies revealed that the complexes 2–4 can catalyze proton reduction
to hydrogen in the presence of HOAc.
Acknowledgments
The authors gratefully acknowledge the support of the Zhejiang
Provincial Natural Science Foundation (No. LY16B020009), the
National Natural Science Foundation of China (No. 21501124),
Science & Technology Department of Sichuan Province (No.
2018JY0235) and the Education Department of Sichuan Province
(No. 18ZA0337).
Appendix A. Supplementary material
CCDC 1821843–1821845 contains the supplementary crystallo-
graphic data. These data can be obtained free of charge via http://
www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ,
UK; fax: (+44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.
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