Synthetic and structural study on some new porphyrin or metalloporphyrin macrocycle-containing model complexes for the active site of [FeFe]-hydrogenases

Article abstract of DOI:10.1016/j.jorganchem.2013.09.007

To mimick the natural enzymes [FeFe]-hydrogenases, some new porphyrin and metalloporphyrin moiety-containing model complexes, namely 5-[p-Fe ₂(CO)₆(μ-SCH₂)₂CHO ₂CC₆H₄],10,15,20-t

Full text of DOI:10.1016/j.jorganchem.2013.09.007

Journal of Organometallic Chemistry 749 (2014) 120e128
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Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Synthetic and structural study on some new porphyrin or
metalloporphyrin macrocycle-containing model complexes for the
active site of [FeFe]-hydrogenases
,
a
a
b
b,
**
Li-Cheng Song a , Liang-Xing Wang , Chang-Gong Li , Fengyu Li , Zhongfang Chen
*
a Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China
b Department of Chemistry, Institute for Functional Nanomaterials, University of Puerto Rico, San Juan, PR 00931-3346, USA
a r t i c l e i n f o
a b s t r a c t
Article history:
To mimick the natural enzymes [FeFe]-hydrogenases, some new porphyrin and metalloporphyrin moiety-
containing model complexes, namely 5-[p-Fe2(CO)6( -SCH2)2CHO2CC6H4],10,15,20-triphenylporphyrin (2),
5-[p-Fe2(CO)6( -SCH2)2CHO2CC6H4],10,15,20-triphenylporphyrinozinc (3), 5-[p-Fe2(CO)6( -SCH2)2NC2H4
SC6H4],10,15,20-triphenylporphyrin (7), and 5-[p-Fe2(CO)5( -SCH2)2NC2H4SC6H],10,15,20-triphenylpor
phyrin (8), have been successfully prepared by our designed synthetic routes involving the correspond-
ing precursor compounds [( -SCH2)2CHO2CC6H4CHO-p]Fe2(CO)6 (1), p-Boc-NHC2H4SC6H4CHO (4), 5-(p-
Boc-NHC2H4SC6H4),10,15,20-triphenylporphyrin (5), and 5-(p-NH2C2H4 SC6H4),10,15,20-triphenylpor
phyrin (6). All these new compounds 1e8 have been characterized by elemental analysis and various
spectroscopic methods, and particularly for 1e3 and 7 by X-ray crystallography. In addition, the density
functional theory computations on 8 were performed to assist its structural characterization.
Ó 2013 Elsevier B.V. All rights reserved.
Received 12 June 2013
Received in revised form
27 August 2013
m
m
m
m
Accepted 5 September 2013
m
Keywords:
Enzyme model
Hydrogenase
Iron
Metalloporphyrin
Porphyrin
Sulfur
1. Introduction
is linked to a butterfly [Fe2S2] cluster via the cysteinyl S atom. In
addition, the two iron atoms of the [Fe2S2] cluster are bridged by a
Hydrogenases are natural enzymes that catalyze the reversible
redox reaction between proton and hydrogen in various microor-
ganisms [1]. According to the metal content in the active site, hy-
drogenases are primarily classified as [FeFe]-hydrogenases ([FeFe]
Hases), [NiFe]-hydrogenases ([NiFe]Hases), and [Fe]-hydrogenases
(Hmd) [2e8]. While [FeFe]Hases are mainly used for proton
reduction to hydrogen, [NiFe]Hases are employed for hydrogen
oxidation to protons [9e11], Hmd is utilized to activate hydrogen
for use in catabolic processes of microorganisms [7,8]. Currently,
[FeFe]Hases are receiving more attention over [NiFe]Hases and
Hmd, because of their unusual structures and particularly their
extremely rapid rates for production of “clean” and highly efficient
H2 fuel [12,13]. Recent X-ray crystallography [14e16] and FTIR
spectroscopy [17e19] revealed that the active site of [FeFe]Hases,
so-called H-cluster [9], consists of a cubane-like [Fe4S4] cluster that
propanedithiolate (PDT), azadithiolate (ADT), or oxadithiolate
(ODT) ligand and are coordinated by a given amount of CO and CNꢀ
ligands (Fig. 1).
Encouraged by the structural studies on H-cluster, the synthetic
chemists have designed and synthesized a variety of structural and
functional models for the active site of [FeFe]Hases [20e38]. Among
these models, the porphyrin or metalloporphyrin-containing
models are of particular interest, since they belong to the dyads
light-driven type models in which the photosensitizer porphyrin or
metalloporphyrin is covalently or coordinatively attached to a
simple diiron model complex. To date, although several such model
complexes have been prepared [34e38], none of them contains the
photosensitizer porphyrinylester or metalloporphyrinylester moi-
ety that is covalently attached to a simple diiron model (such as 2
and 3 in Fig. 2) or includes a porphyrinylthioether moiety that is
covalently or coordinatively bound to a simple diiron model (such
as 7 and 8 in Fig. 2). To develop the synthetic methodology for such
new types of porphyrin or metalloporphyrin-containing H-cluster
model complexes, we initiated this study. Herein we report the
results of this study.
* Corresponding author.
** Corresponding author.
E-mail addresses: lcsong@nankai.edu.cn (L.-C. Song), zhongfangchen@
gmail.com (Z. Chen).
0022-328X/$ e see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jorganchem.2013.09.007

L.-C. Song et al. / Journal of Organometallic Chemistry 749 (2014) 120e128
121
and one absorption band in the range 1706e1722 cmꢀ1 for their
organic carbonyls, respectively. In addition, 2 and 3 showed three
absorption bands in the region 1558e1339 cmꢀ1 assigned to the
skeleton vibrations of pyrrole rings in their porphyrin and por-
phyrinozinc macrocycles, respectively [40]. The 1H NMR spectra of
1e3 showed a broad singlet or a multiplet at about 4.6 ppm for
their bridgehead C-attached axial hydrogen atoms, whereas 2
exhibited a singlet at ꢀ2.80 ppm for the two protons attached to N
atoms in its pyrrole rings [41]. The UVevis spectra of 2 and 3 were
determined in CH2Cl2, which showed one Soret band at 412 and
414 nm in the near-UV region, respectively. In addition, 2 dis-
played four Q bands in the range 514e645 nm, whereas 3
exhibited two Q bands at 548 and 586 nm in the visible region.
Apparently, the different Q bands displayed by 2 and 3 are caused
by the different photosensitizer moieties [34,35], namely the
porphyrinylester moiety for 2 and the metalloporphyrinylester
moiety for 3.
Fig. 1. The simplified structure of H-cluster in different functional states (L ¼ H2O, CO,
H, or H2; X ¼ CH2, NH, or O).
2. Results and discussion
2.1. Synthesis and spectroscopic characterization of simple model
complex [(m-SCH2)2CHO2CC6H4CHO-p]Fe2(CO)6] (1) and the porphyrin
2.2. Crystal structures of 1e3
or metalloporphyrin-containing model complexes 5-[p-Fe2(CO)6(m-
SCH2)2CHO2CC6H4],10,15,20-triphenylporphyrin (2) and 5-[p-
Fe2(CO)6(m-SCH2)2CHO2CC6H4],10,15,20-triphenylporphyrinozinc (3)
The molecular structures of 1e3 were unambiguously
confirmed by X-ray diffraction techniques (Fig. 3e5, Table 1e3). As
can be seen intuitively from Fig. 3, complex 1 contains a diiron PDT
moiety in which the six-membered ring Fe1S1C7C8C9S2 has a chair
conformation and the other six-membered ring Fe2S1C7C8C9S2 a
boat conformation. The p-formylbenzoate group is attached to the
common C8 atom of the two six-membered rings by an equatorial
bond and a hydrogen atom is attached to C8 by an axial bond. Both
Fe1 and Fe2 atoms adopt the expected square-pyramidal geometry
According to our designed synthetic route for preparation of the
porphyrinylester or metalloporphyrinylester moiety-containing
model complexes 2 and 3, we should first prepare the simple p-
formylbenzoate functionalized model complex 1. The treatment of
the C-hydroxy functionalized complex [(m-SCH2)2CH(OH)]Fe2(CO)6
with p-formylbenzoyl chloride (prepared in situ by reaction of p-
formylbenzoic acid with SOCl2) [39] in CH2Cl2 in the presence of
Et3N gave the simple model complex 1 in 62% yield. Further
treatment of 1 with benzaldehyde and pyrrole in 1:3:4 M ratio in
the presence of BF3$OEt2, followed by treatment with oxidant p-
chloranil afforded model complex 2 in 21% yield along with tetra-
phenylporphyrin (TPP) in 18% yield. Finally, the metal-
loporphyrinylester moiety-containing model complex
produced by reaction of 2 in CHCl3 with Zn(OAc)2 in MeOH at room
temperature in 88% yield (Scheme 1).
ꢀ
and the Fe1eFe2 bond length (2.5007 A) is very close to the cor-
responding those of its parent complex [(
m-SCH2)2CH(OH)]Fe2(CO)6
and similar diiron complexes [26,42e44].
Fig. 4 shows that complex 2 has the same diiron PDT moiety as 1,
but the equatorial p-formylbenzoate group in 1 has been replaced
by an equatorial porphyrinylester moiety. In the porphyrin cycle the
CeN bond lengths in pyrrole rings are nearly the same (1.366e
3 was
ꢀ
1.380 A), which lie between those of normal single and double CeN
bonds [45]. It is worth pointing out that the four benzene rings
attached to porphyrin cycle is planar and twisted relative to the
porphyrin plane in order to reduce the steric interactions between
the phenyl hydrogen atoms proximal to the porphyrin cycle and the
pyrrole rings.
Complexes 1e3 are air-stable red solids, which have been
characterized by elemental analysis and spectroscopy. For
instance, the IR spectra of 1e3 displayed three to four absorption
bands in the region 2075e1992 cmꢀ1 for their terminal carbonyls
Fig. 2. The target light-driven models 2, 3, 7, and 8 reported in this article.

122
L.-C. Song et al. / Journal of Organometallic Chemistry 749 (2014) 120e128
Scheme 1. Synthetic routes of 1e3.
As can be seen in Fig. 5, the structure of 3 is almost identical with
in 25% and 20% yields, respectively. Precursor 6 was obtained in 86%
yield by removal of the Boc group from 5, which was realized by
treating 5 with a HCl (2 mol Lꢀ1) solution in 1:1 (v/v) THF and AcOEt
(Scheme 2).
With the availability of precursors 4e6, we started to prepare
the target model complexes 7 and 8 by a sequential reaction
that of 2, except the parent porphyrin macrocycle is replaced by a
porphyrinozinc macrocycle. It is noteworthy that in the structure of
3 there is one molecule of MeOH axially coordinated to Zn1 atom
ꢀ
with a Zn1eO9 bond length of 2.116 A. The coordinated MeOH was
obviously originated from the mixed solvent o-Cl2C6H4/MeOH used
in the single-crystal growing process. The Fe1eFe2 bond length
involving (i) reaction of (m-S2)Fe2(CO)6 with LiBEt3H in THF
(2.5077 A) is very close to the corresponding those of its parent
at ꢀ78 ꢁC followed by treating (
m-LiS)2Fe2(CO)6 with CF3CO2H to
give (m-HS)2Fe2(CO)6 [46]; (ii) in situ reaction of (m-HS)2Fe2(CO)6
ꢀ
complex and similar diiron complexes [26,42e44]. The four ben-
zene rings around the metalloporphyrin moiety are also twisted
relative to the porphyrin plane with a dihedral angle from 66.8ꢁ to
87.2ꢁ in order to reduce the steric repulsions between the proximal
hydrogen atoms of the benzene and pyrrole rings in the metal-
loporphyrin macrocycle.
with 40% aqueous formaldehyde in THF from ꢀ78 ꢁC to room
temperature to yield (m-HOCH2S)2Fe2(CO)6 [47]; (iii) in situ reaction
of (m-HOCH2S)2Fe2(CO)6 with 6 to afford model 7 in 51% yield; and
(iv) final reaction of the isolated 7 with decarbonylating agent
Me3NO$2H2O in CH2Cl2/MeCN at room temperature to produce
model 8 in 88% yield (Scheme 3).
Precursors 4e6 are all air-stable solids, which have been char-
acterized by elemental analysis and spectroscopic techniques. For
example, the IR spectrum of 4 showed two absorption bands at
1682 and 1691 cmꢀ1 for its aldehyde and ester carbonyl groups,
whereas 5 and 6 exhibited three absorption bands in the range of
1558e1349 cmꢀ1 for the skeleton vibrations of the pyrrole rings in
their porphyrin moieties [40]. The 1H NMR spectrum of 4 displayed
a singlet at 9.93 ppm for its benzaldehyde CHO group, whereas 5
and 6 exhibited a singlet at ꢀ2.78 and ꢀ2.77 ppm for the NH groups
in their porphyrin moieties [41]. In addition, the 1H NMR spectra of
4 and 5 displayed a singlet at 4.90 and 5.09 ppm for the NH groups
attached to their ester carbonyls, whereas 6 showed a singlet at
2.50 ppm for its NH2 group.
2.3. Synthesis and spectroscopic characterization of precursor
compounds p-Boc-NHC2H4SC6H4CHO (4), 5-(p-Boc-NHC2H4SC6H4),
10,15,20-triphenylporphyrin (5), 5-(p-NH2C2H4SC6H4),10,15,20-
triphenylporphyrin (6), and the porphyrin-containing model complexes 5-
[p-Fe2(CO)6(m-SCH2)2NC2H4SC6H4],10,15,20-triphenylporphyrin (7) and
5-[p-Fe2(CO)5(m-SCH2)2NC2H4SC6H4],10,15,20-triphenylporphyrin (8)
In order to prepare the designed two porphyrinylthioether-
containing model complexes 7 and 8, we first prepared their pre-
cursor compounds 4e6. The treatment of Boc-NHC2H4SH
(Boc ¼ tert-butoxycarbonyl) with KOH in EtOH and subsequent
treatment of the resulting potassium mercaptide Boc-NHC2H4SK
with p-ClC6H4CHO resulted in formation of precursor 4 in 50% yield.
Further treatment of 4 with benzaldehyde, pyrrole, and BF3$OEt2 in
CH2Cl2 at room temperature, followed by treatment of the resulting
mixture with the oxidant p-chloranil afforded TPP and precursor 5
Complexes 7 and 8 are also air-stable solids, which have been
characterized by elemental analysis and spectroscopy. The IR
spectra of 7 and 8 showed three to five absorption bands in the
Table 1
Table 2
ꢁ
ꢁ
ꢀ
ꢀ
Selected bond lengths (A) and angles ( ) for 1.
Selected bond lengths (A) and angles ( ) for 2.
Bond lengths
Bond lengths
Fe(1)eS(2)
Fe(1)eC(1)
Fe(2)eS(2)
O(8)eC(10)
2.2555(7)
1.806(3)
2.2490(7)
1.999(3)
Fe(1)eS(1)
Fe(1)eFe(2)
Fe(2)eS(1)
O(9)eC(17)
2.2430(7)
2.5007(5)
2.2618(7)
1.201(3)
Fe(1)eS(1)
Fe(1)eS(2)
Fe(2)eS(1)
N(1)eC(18)
2.2680(15)
2.2701(14)
2.2491(15)
1.380(6)
Fe(2)eS(2)
C(8)eO(7)
Fe(1)eFe(2)
C(14)eC(17)
2.2560(14)
1.467(5)
2.5071(11)
1.508(6)
Bond angles
Bond angles
Fe(2)eFe(1)eS(1)
Fe(1)eFe(2)eS(2)
S(1)eFe(2)eS(2)
Fe(2)eS(1)eFe(1)
56.640(18)
56.403(18)
84.68(2)
Fe(2)eFe(1)eS(2)
Fe(1)eFe(2)eS(1)
Fe(1)eS(2)eFe(2)
C(7)eC(8)eO(7)
56.153(19)
55.922(19)
67.444(19)
106.88(17)
S(1)eFe(1)eS(2)
S (1)eFe(1)eFe(2)
S(1)eFe(2)eS(2)
Fe(2)eS(2)eFe(1)
84.62(5)
55.93(4)
85.39(5)
67.27(4)
C(21)eN(1)eC(18)
C(23)eN(2)eC(26)
S(2)eFe(1)eFe(2)
Fe(2)eS(1)eFe(1)
109.6(4)
106.6(4)
56.10(4)
67.42(5)
67.439(19)

L.-C. Song et al. / Journal of Organometallic Chemistry 749 (2014) 120e128
123
Table 3
ꢁ
ꢀ
Selected bond lengths (A) and angles ( ) for 3.
Bond lengths
Fe(1)eS(1)
Fe(1)eS(2)
Fe(2)eS(2)
Fe(2)eS(1)
2.252(3)
2.244(2)
2.246(2)
2.273(2)
Zn(1)eN(1)
2.061(6)
2.5077(17)
1.474(8)
Fe(1)eFe(2)
C(46)eO(2)
N(1)eC(41)
1.390(8)
Bond angles
N(2)eZn(1)eN(1)
S(1)eFe(1)eFe(2)
O(2)eC(46)eC(47)
N(1)eZn(1)eN(3)
88.8(2)
56.74(7)
106.6(5)
164.1(2)
S(1)eFe(1)eS(2)
S(1)eFe(2)eS(2)
S(1)eFe(2)eFe(1)
C(41)eN(1)eC(44)
85.68(9)
85.13(9)
55.94(7)
107.4(6)
range of 2070e1935 cmꢀ1 assigned to their terminal carbonyls, and
three absorption bands in the region 1558e1348 cmꢀ1 attributed to
the skeletal vibrations of the pyrrole rings in their porphyrin
moieties [40]. In addition, the 1H NMR spectrum of 7 displayed two
triplets at 3.10 and 3.23 ppm for the two CH2 groups between the
bridgehead N atom and the S atom attached to porphyrin moiety,
whereas 8 exhibited two doublets at 3.29 and 3.69 ppm for the
corresponding two CH2 groups, respectively. Note that the 1H NMR
signals for the two CH2 groups of 8 is shifted downfield by ca. 0.2e
0.5 ppm compared to those corresponding to 7. This is obviously
because the S atom in 8 is coordinated to Fe atom and in turn to
cause the decrease of the electron density around the two CH2
groups. In addition, the 1H NMR spectra of 7 and 8 displayed a
singlet at ca. ꢀ2.7 ppm for the NH groups in their pyrrole rings due
to strong shielding effects of the porphyrin macrocycle [41]. The
UVevis spectra of 7 and 8 determined in CH2Cl2 all showed one
Soret band at 418 nm in the near-UV region. In addition, 7 and 8
displayed almost identical four Q bands at 515, 550, 591, and
Fig. 4. ORTEP view of 2 with 30% probability level ellipsoids.
645 nm for 7 and at 514, 550, 591, and 645 nm for 8 in the visible
region. This is because they contain the same photosensitizer por-
phyrinylthioether moiety and the coordination mode of this
photosensitizer, either covalently or coordinatively, has no actual
influence upon their UVevis spectra.
2.4. Crystal structure of 7 and DFT computations on 8
The molecular structure of model complex 7 was unequivocally
confirmed by X-ray diffraction analysis. While the ORTEP view of
model complex 7 is presented in Fig. 6, Table 4 lists its selected
bond lengths and angles.
Similar to the previously reported porphyrin-containing ADT-
type model complexes [34e36], complex 7 was unequivocally
confirmed to contain a diiron-ADT unit in which a boat-shaped six-
membered ring N1C7S2Fe1S1C8 is fused to a chair-shaped six-
membered ring N1C7S2Fe2S1C8. The diiron-ADT unit is connected
via its bridgehead N1 atom to C11 atom of the porphyrin moiety
(Note that N1eC9 is the common axial bond of the two fused six-
membered rings). In the porphyrin moiety, the four benzene
rings are twisted relative to the porphyrin plane with a dihedral
angle from 56.3 to 83.2ꢁ in order to reduce the strong steric re-
pulsions between the phenyl hydrogen atoms proximal to
porphyrin moiety and the pyrrole rings. In addition, the porphyrin
plane is nearly perpendicular to the S1S2C7C8 plane with a dihe-
dral angle of 84.6ꢁ. While the CeN bond lengths in pyrrole rings of
ꢀ
the porphyrin moiety are almost the same (1.366e1.379 A) and are
Fig. 3. ORTEP view of 1 with 30% probability level ellipsoids.
between those of normal single and double CeN bonds [45], the

124
L.-C. Song et al. / Journal of Organometallic Chemistry 749 (2014) 120e128
ꢀ
and [(m-SCH2)2NCH(CO2Et)CH2SFe(CO)2Cp]Fe2(CO)5 (2.299 A) [49].
Finally, it is interesting to note that the coordination mode of the
porphyrinylthioether with diiron subsite in 8 is very similar to that
of the [Fe4S4] cluster and [Fe2S2] cluster in the natural enzymes.
3. Experimental section
All reactions were performed using standard Schlenk and
vacuum-line techniques under an atmosphere of nitrogen.
Dichloromethane was distilled under N2 over CaH2, absolute
ethanol from freshly prepared magnesium ethoxide, THF from so-
dium/benzophenone ketyl, and MeCN once from P2O5 and then
from CaH2. While Boc-NHC2H4SH [50], (m-S2)Fe2(CO)6 [51] and (m-
SCH2)2CH(OH)Fe2(CO)6 [44] were prepared according to literature
procedures, LiBEt3H (1 M in THF), Me3NO$2H2O, BF3$OEt2, pyrrole,
benzaldehyde, 2,3,5,6-tetrachlorobenzoquinone (p-chloranil),
CF3CO2H, p-CHOC6H4CO2H, and p-ClC6H4CHO were of commercial
origin. Preparative TLC was carried out on glass plates
(26 ꢂ 20 ꢂ 0.25 cm) coated with silica gel H (10e40
mm) or fluo-
rescence silica gel GF254 (10e40 m). IR spectra were recorded on a
m
Bruker Vector 22 infrared spectrophotometer. UVevis spectra were
taken on a Varian CARY 100 Bio spectrophotometer. 1H NMR
spectra were recorded on a Varian Mercury Plus 400 NMR spec-
trometer. Elemental analyses were performed on an Elementar
Vario EL analyzer. Melting points were determined on a Yanaco MP-
500 apparatus and are uncorrected.
3.1. Preparation of [(m-SCH2)2CHO2CC6H4CHO-p]Fe2(CO)6 (1)
Fig. 5. ORTEP view of 3 with 30% probability level ellipsoids.
To a stirred suspension of p-CHOC6H4CO2H (0.30 g, 2.0 mmol) in
benzene (10 mL) was added SOCl2 (0.6 mL, 8.0 mmol) and then the
mixture was refluxed for 3 h. Solvent was removed at reduced
pressure to give the corresponding acid chloride p-CHOC6H4COCl,
which was dissolved in CH2Cl2 (10 mL). To this solution was added
Et3N (0.4 mL, 2.0 mmol) and then the mixture was treated at 0 ꢁC
ꢀ
Fe1eFe2 bond length (2.511 A) is slightly shorter than the corre-
sponding bond length in the reduced state of the natural enzyme
ꢀ
(2.55 A) [16].
Since the crystal structure of model complex 8 was not obtained
due to lack of the qualified single-crystal for X-ray diffraction
analysis, we performed the density functional theory (DFT) com-
putations to assist its structural characterization. Fig. 7 shows the
DFT optimized molecular structure of 8, whereas some of the
calculated bond lengths and angles are given in Table 5. As can be
seen in Table 5, the calculated bond lengths and angles of 8 are very
close to the corresponding those of 7 determined by X-ray
diffraction analysis. In addition, the calculated Fe1eS3 bond length
(2.275 A) of 8 (namely the distance between its thioether S atom
and one Fe atom in its diiron subsite) is very close to the corre-
sponding FeeS bond lengths of the previously reported simple
model complexes, such as [(m-SCH2)2NCH2CH2SMe]Fe2(CO)5
dropwise with a solution of [(m-SCH2)2CH(OH)]Fe2(CO)6 (0.80 g,
2.0 mmol) in CH2Cl2 (60 mL). After the new mixture was stirred at
room temperature for 2 h, it was washed three times with water
(20 ꢂ 3 mL). The separated organic layers were combined and dried
over anhydrous Na2SO4. After Na2SO4 and solvent were removed,
the residue was subjected to TLC separation using petroleum ether/
CH2Cl2 (2:1 ¼ v/v) as eluent. From the major red band, 1 was ob-
tained as a red solid (0.662 g, 62%), m.p. 162e164 ꢁC. Anal. Calcd for
ꢀ
C17H10Fe2O9S2: C, 38.27; H, 1.89. Found: C, 38.22; H, 1.84. IR (KBr
disk): nC
^
cmꢀ1. 1H NMR (400 MHz, CDCl3):
O 2075 (s), 2035 (vs), 2018 (vs), 1992 (vs); nC
]
O 1706 (s)
0
d
¼ 1.72 (t, 2Ha, JHaHe ¼ JHaHa
¼
ꢀ
ꢀ
(2.270 A) [26], [(m-SCH2)2C(Me)CH2SMe]Fe2(CO)5 (2.254 A) [48]
0
12.0 Hz), 2.92e2.96 (m, 2He), 4.50 (br. s, 1Ha ), 7.92 (d, 2H, J ¼ 7.6 Hz,
Scheme 2. Synthetic routes of 4e6.

L.-C. Song et al. / Journal of Organometallic Chemistry 749 (2014) 120e128
125
Scheme 3. Synthetic routes of 7 and 8.
2m-H of C6H4CHO), 8.10 (d, 2H, J ¼ 7.6 Hz, 2o-H of C6H4CHO), 10.09
BF3$OEt2 (0.041 mL, 0.33 mmol) was added. After the new mixture
was stirred in the dark for 15 h, 2,3,5,6-tetrachlorobenzoquinone (p-
chloranil) (0.80 g, 3.28 mmol) was added. The mixture refluxed in
the dark for 1.5 h and then was cooled to room temperature. After
the mixture was concentrated to about 1/3 volume at reduced
pressure, the residue was subjected to flash column chromatog-
raphy (Al2O3, CH2Cl2) and then the eluate was concentrated to a
suitable volume for TLC separation. From the first purple band using
CH2Cl2/petroleum ether (1:2 ¼ v/v) as eluent, TPP (0.098 g,18%) was
obtained as a purple solid, which was identified by comparison of its
IR and 1H NMR spectra with those of the authentic sample [40,41].
From the second purple band using CH2Cl2/petroleum ether (1:1 v/
v) as eluent, 2 (0.178 g, 21%) as a purple solid was obtained. m.p.
174 ꢁC (dec). Anal. Calcd for C54H34Fe2N4O8S2: C, 62.20; H, 3.29; N,
(s, 1H, CHO) ppm (In this paper Ha and He denote the axially and
0
equatorially bonded H atoms in CH2S groups, while Ha represents
that axially bonded to bridgehead C atom).
3.2. Preparation of 5-[p-Fe2(CO)6(m-SCH2)2CHO2C6H4],10,15,20-
triphenylporphyrin (2)
To a stirred solution of 1 (0.437 g, 0.82 mmol), benzaldehyde
(0.25 mL, 2.46 mmol) in CHCl3 (300 mL) was added pyrrole (0.23 mL,
3.28 mmol). After the mixture was stirred in the dark for 15 min
5.37. Found: C, 61.96; H, 3.28; N, 5.35. IR (KBr disk): nC^O 2075 (s),
2035 (vs), 1998 (vs); nC]O 1722 (s); npyrrole rings 1558 (m), 1473 (m),
1344 (m) cmꢀ1. 1H NMR (300 MHz, CDCl3):
d
¼ ꢀ2.80 (s, 2H, 2NH of
0
pyrrole rings), 1.86 (t, 2Ha, JHaHe ¼ JHaHa ¼ 12.2 Hz), 3.11 (dd, 2He,
0
0
JHeHa ¼ 12.6 Hz, JHeHa ¼ 4.2 Hz), 4.63e4.73 (m, 1Ha ), 7.73e7.78 (m,
9H, 6 m-H of 3C6H5, 3 p-H of 3C6H5), 8.19e8.23 (m, 6H, 6 o-H of
3C6H5), 8.29, 8.34 (dd, 4H, AB system, J ¼ 8.4 Hz, C6H4), 8.72e8.85
(m, 8H, 8CH of pyrrole rings) ppm. UVevis (CH2Cl2): lmax
(log ε) ¼ 412 (5.09), 514 (4.27), 549 (3.90), 589 (3.73), 645 (3.59) nm.
Table 4
ꢁ
ꢀ
Selected bond lengths (A) and angles ( ) for 7.
Bond lengths
Fe(1)eS(1)
Fe(1)eS(2)
S(1)eC(8)
S(2)eC(7)
2.2671(14)
2.2673(14)
1.874(4)
Fe(1)eFe(2)
Fe(2)eS(1)
Fe(2)eS(2)
S(3)eC(11)
2.5109(11)
2.2637(15)
2.2524(15)
1.786(4)
1.865(4)
Bond angles
S(1)eFe(1)eS(2)
S(1)eFe(1)eFe(2)
Fe(1)eS(1)eFe(2)
C(8)eS(1)-Fe(1)
84.52(5)
56.28(4)
67.31(4)
C(8)eS(1)eFe(2)
N(1)eC(9)eC(10)
C(9)eC(10)eS(3)
C(11)eS(3)eC(10)
110.42(17)
111.6(4)
115.6(3)
107.2(2)
112.13(16)
Fig. 6. ORTEP view of 7 with 30% probability level ellipsoids.

126
L.-C. Song et al. / Journal of Organometallic Chemistry 749 (2014) 120e128
3.4. Preparation of p-Boc-NHC2H4SC6H4CHO (4)
A solution of KOH (1.13 g, 20.2 mmol) in EtOH (25 mL) at 0 ꢁC
was treated dropwise with a solution of Boc-NHC2H4SH (3.54 g,
20.0 mmol) in EtOH (5 mL). After the mixture was stirred at 0 ꢁC for
30 min, p-ClC6H4CHO (2.70 g, 19.2 mmol) was added, and then the
new mixture was stirred at 75e78 ꢁC for 3 h, resulting in a pale
yellow solution with some KCl precipitates. To this mixture was
added water (70 mL), and then the resulting solution was extracted
with CCl4 (20 mL ꢂ 4). After CCl4 was removed from the extracts in
vacuum, the residue was subjected to fluorescence TLC separation
using acetone/petroleum ether (1:5 ¼ v/v) as eluent. From the
major band, 4 was obtained as a white solid (2.69 g, 50%), m.p. 51e
52 ꢁC. Anal. Calcd for C14H19NO3S: C, 59.76; H, 6.81; N, 4.98. Found:
C, 59.70; H, 6.70; N, 5.07. IR (KBr disk): nC
] 1691 (vs), 1682 (s)
O
cmꢀ1. 1H NMR (400 MHz, CDCl3):
d
¼ 1.44 (s, 9H, C(CH3)3), 3.17 (t,
2H, J ¼ 6.4 Hz, NCH2CH2S), 3.40, 3.42 (2s, 2H, NCH2CH2S), 4.90 (s,
1H, NH), 7.42 (d, 2H, J ¼ 8.0 Hz, 2m-H of C6H4CHO), 7.78 (d, 2H,
J ¼ 8.4 Hz, 2o-H of C6H4CHO), 9.93 (s, 1H, CHO) ppm.
Fig. 7. Fully optimized structure of 8. The gray, cyan, red, yellow, blue and pale balls
denote carbon, iron, oxygen, sulfur, nitrogen, and hydrogen atoms, respectively. (For
interpretation of the references to color in this figure legend, the reader is referred to
the web version of this article.)
3.5. Preparation of 5-(p-Boc-NHC2H4SC6H4),10,15,20-triphenylporphrin
(5)
A solution of 4 (0.30 g, 1.1 mmol), pyrrole (0.28 mL, 4.0 mmol),
PhCHO (0.30 mL, 3.0 mmol), and BF3$OEt2 (0.05 mL, 0.40 mmol) in
CH2Cl2 (400 mL) was stirred in the dark at room temperature for
16 h to give a purple solution. To this solution was added p-chloranil
(0.984 g, 4.0 mmol), and then the new mixture was heated at reflux
for 2 h to give a brown solution. After solvent was removed at
reduced pressure, the residue was subjected to flash column
chromatography (Al2O3, CH2Cl2). The eluate was reduced to a
suitable volume for TLC separation by using CH2Cl2/petroleum
ether (12:1 ¼ v/v) as eluent. From the first purple band, TPP (0.115 g,
25%) was obtained as a purple solid, which was identified by
comparison of its IR and 1H NMR spectra with those of the
authentic sample [40,41]. From the second purple-red band, 5 was
obtained as a purple solid (0.154 g, 20%), m.p. 244e246 ꢁC. Anal.
Calcd for C51H43N5O2S: C, 77.54; H, 5.49; N, 8.87. Found: C, 77.42; H,
3.3. Preparation of 5-[p-Fe2(CO)6(m-SCH2)2CHO2CC6H4],10,15,20-
triphenylporphyrinozinc (3)
To a solution of 2 (0.042 g, 0.04 mmol) in CHCl3 (20 mL) was
added MeOH solution (2 mL) of Zn(OAc)2$2H2O (0.57 g,
a
0.26 mmol). After the mixture was refluxed for 2 h and then cooled
to room temperature, the resulting mixture was filtered and the
filtrate was sequentially washed using an aqueous solution satu-
rated with NaHCO3 and NaCl. The separated organic layers were
combined and dried with anhydrous MgSO4. After removal of
MgSO4, volatiles were evaporated under vacuum and the residue
was subjected to TLC using CH2Cl2/petroleum ether (3:2 ¼ v/v) as
eluent. From the main band, 3 (0.039 g, 88%) was obtained as a
purple solid, m.p. 196 ꢁC (dec). Anal. Calcd for C54H32Fe2N4O8S2Zn:
C 58.64; H, 2.92; N, 5.07. Found: C, 58.41; H, 2.68; N, 5.17. IR (KBr
5.52; N, 8.91. IR (KBr disk): nC
] 1715 (vs); npyrrole rings 1558 (m),
O
disk): nC
^ 2075 (s), 2036 (vs), 2000 (vs); nC] 1720 (s); npyrrole
O
O
1473 (s), 1349 (m) cmꢀ1. 1H NMR (400 MHz, CDCl3):
d
¼ ꢀ2.78 (s,
rings 1558 (m), 1487 (m), 1339 (m) cmꢀ1. 1H NMR (400 MHz, CDCl3):
2H, 2NH of pyrrole rings), 1.49 (s, 9H, C(CH3)3), 3.31 (t, 2H,
J ¼ 6.0 Hz, NCH2CH2S), 3.58, 3.59 (2s, 2H, NCH2CH2S), 5.09 (s, 1H,
Boc-NH), 7.70e7.75 (m, 11H, 2o-H of SC6H4, 6m-H of 3C6H5, 3p-H of
3C6H5), 8.13, 8.14 (2s, 2H, 2m-H of SC6H4), 8.20, 8.22 (2s, 6H, 6o-H of
3C6H5), 8.85 (s, 8H, 8CH of pyrrole rings) ppm.
0
d
¼ 1.86 (t, 2Ha, JHaHe ¼ JHaHa ¼ 12.2 Hz), 0 3.11 (dd, 2He,
0
JHeHa ¼ 12.8 Hz, JHeHa ¼ 4.0 Hz), 4.64e4.72 (m, 1Ha ), 7.73e7.78 (m,
9H, 6 m-H of 3C6H5, 3 p-H of 3C6H5), 8.19e8.23 (m, 6H, 6 o-H of
3C6H5), 8.28, 8.35 (dd, 4H, AB system, J ¼ 8.0 Hz, C6H4), 8.82e8.97
(m, 8H, 8CH of pyrrole rings) ppm. UVevis (CH2Cl2): lmax
(log ε) ¼ 414 (5.08), 548 (4.46), 586 (3.57) nm.
3.6. Preparation of 5-(p-NH2C2H4SC6H4),10,15,20-triphenylporphrin
(6)
Table 5
ꢁ
ꢀ
Selected bond lengths (A) and angels ( ) for 8 based on BP86/6-311þG** geometry.
To a solution of HCl (2 mol Lꢀ1) in THF/ethyl acetate (20 mL, 1:1
in volume) was added 5 (0.166 g, 0.21 mmol), and then the mixture
was stirred at 30 ꢁC for about 2 h. After volatiles were removed at
reduced pressure, the green residue was redissolved in CHCl3
(40 mL) and washed sequentially with saturated aqueous NaHCO3
(40 mL) and aqueous NaCl (10 mL). After CHCl3 was removed at
reduced pressure, the purple residue was subjected to TLC sepa-
ration using CH2Cl2/ethanol (10:1 ¼ v/v) as eluent to give 6 as a
purple solid (0.125 g, 86%), m.p. 196 ꢁC (dec). Anal. Calcd for
Bond lengths
Fe(1)eS(1)
Fe(1)eS(2)
Fe(1)eS(3)
S(1)eC(6)
S(2)eC(7)
S(3)eC(9)
S(3)eC(10)
2.312
2.300
2.275
1.908
1.900
1.858
1.814
Fe(1)eFe(2)
Fe(2)eS(1)
Fe(2)eS(2)
N(1)eC(6)
N(1)eC(7)
N(1)eC(8)
C(13)eC(16)
2.533
2.308
2.306
1.427
1.431
1.463
1.500
Bond angles
S(1)eFe(1)eS(2)
S(1)eFe(2)eS(2)
S(1)eFe(1)eFe(2)
S(2)eFe(1)eFe(2)
S(1)eFe(2)eFe(1)
S(2)eFe(2)eFe(1)
Fe(1)eS(1)eFe(2)
Fe(1)eS(2)eFe(2)
85.84
85.81
56.67
56.74
56.83
56.54
66.50
66.73
C(10)eS(3)eFe(1)
C(9)eS(3)eFe(1)
C(9)eS(3)eC(10)
S(3)eFe(1)eC(1)
C(6)eN(1)eC(7)
C(6)eS(1)eFe(1)
C(7)eS(2)eFe(2)
C(8)eC(9)eS(3)
113.01
109.08
100.01
103.97
115.38
111.78
110.08
111.80
C
46H35N5S: C, 80.09; H, 5.11; N, 10.15. Found: C, 79.98; H, 5.19; N,
10.09. IR (KBr disk): npyrrole rings 1558 (m), 1472 (s), 1349 (m) cmꢀ1
1H NMR (400 MHz, CDCl3):
.
d
¼ ꢀ2.77 (s, 2H, 2 NH of pyrrole rings),
2.50 (br. s, 2H, NH2), 3.22, 3.24 (2s, 2H, NCH2CH2S), 3.33 (t, 2H,
J ¼ 5.6 Hz, NCH2CH2S), 7.70e7.78 (m, 11H, 2o-H of SC6H4, 6m-H of
3C6H5, 3p-H of 3C6H5), 8.13, 8.15 (2s, 2H, 2m-H of SC6H4), 8.23 (s,
6H, 6o-H of 3C6H5), 8.87 (s, 8H, 8CH of pyrrole rings) ppm.

L.-C. Song et al. / Journal of Organometallic Chemistry 749 (2014) 120e128
127
Table 6
Crystal data and structure refinements details for 1e3 and 7.
1
2
3
7
Formula
C17H10Fe2O9S2
534.07
Triclinic
P1
7.5740(10)
8.8550(14)
16.512(2)
92.697(7)
93.435(6)
110.481(8)
1032.8(3)
2
C54H34Fe2N4O8S2$2CH2Cl
1127.60
Monoclinic
P121/a1
12.8588(10)
8.9807(6)
43.103(3)
90
96.443(4)
90
4946.1(6)
4
C54H32Fe2N4O8S2Zn$2CH3OH$1.5o-Cl2C6H4
C54H37Fe2N5O6S3
1059.77
Triclinic
P1
10.640(4)
12.649(4)
17.847(6)
94.988(6)
92.298(6)
91.862(7)
2389.3(14)
2
Formula weight
Crystal syst
Space group
1390.60
Monoclinic
P1
ꢀ
a (A)
9.724(4)
13.185(5)
23.990(9)
93.391(2)
94.266(4)
98.248(7)
3028(2)
2
ꢀ
b (A)
ꢀ
c (A)
a
b
g
(ꢁ)
(ꢁ)
(ꢁ)
3
ꢀ
V (A )
Z
Dc (g cmꢀ3
)
1.717
1.653
1.514
0.841
1.524
1.131
1.473
0.796
m
(Mo-K
a
) (mmꢀ1
)
F(000)
536.00
2304
1418
1088
Limiting indices
ꢀ9 ꢃ h ꢃ 9
ꢀ7 ꢃ k ꢃ 11
ꢀ21 ꢃ l ꢃ 21
7869
ꢀ15 ꢃ h ꢃ 14
ꢀ10 ꢃ k ꢃ 10
ꢀ51 ꢃ l ꢃ 51
32,173
ꢀ11 ꢃ h ꢃ 11
ꢀ15 ꢃ k ꢃ 15
ꢀ28 ꢃ l ꢃ 28
22,946
ꢀ12 ꢃ h ꢃ 12
ꢀ15 ꢃ k ꢃ 15
ꢀ19 ꢃ l ꢃ 21
24,718
No. of rflns
No. of indep rflns
2
4826
55.74
8572
50.00
10,480
50.04
8409
50.02
qmax (ꢁ)
R
0.0316
0.0749
0.0934
0.0664
Rw
0.0738
0.1718
0.1978
0.1589
Goodness-of-fit
Largest diff peak and hole (e A
0.955
0.311/ꢀ0.424
1.160
0.415/ꢀ1.135
1.102
1.059/ꢀ1.242
1.102
0.529/ꢀ0.431
ꢀꢀ3
)
3.7. Preparation of 5-[p-Fe2(CO)6(
triphenylporphyrin] (7)
m
-SCH2)2NC2H4SC6H4],10,15,20-
band, 8 (0.010 g, 88%) was obtained as a purpleered solid, m.p.
148 ꢁC (dec). Anal. Calcd for C53H37Fe2N5O5S3: C, 61.70; H, 3.61; N,
6.79. Found: C, 61.61; H, 3.71; N, 6.75. IR (KBr disk): nC
2044 (vs), 2032 (vs), 1984 (vs), 1935 (m); npyrrole rings 1558 (m), 1472
(s),1349 (m) cmꢀ1. 1H NMR (400 MHz, CDCl3):
of pyrrole rings), 3.29 (s, 2H, NCH2CH2S), 3.68 (s, 2H, NCH2CH2S),
4.11 (s, 4H, N(CH2S)2), 7.76, 7.78 (2s, 9H, 6m-H of 3C6H5, 3p-H of
3C6H5) 8.18e8.23 (m, 8H, 2o-H of SC6H4, 6o-H of 3C6H5), 8.36, 8.38
(2s, 2H, 2m-H of SC6H4), 8.83e8.90 (m, 8H, 8CH of pyrrole rings)
ppm. UVevis (CH2Cl2): lmax (log ε) ¼ 418 (4.59), 514 (3.33), 550
(3.08), 591 (2.93), 645 (2.84) nm.
^O 2070 (s),
A red solution of (m-S)2Fe2(CO)6 (0.034 g, 0.10 mmol) in THF
(10 mL) was cooled to ꢀ78 ꢁC, and then treated dropwise with
d
¼ ꢀ2.77 (s, 2H, 2NH
Et3BHLi (0.20 mL, 0.20 mmol) to give a green solution containing
(m
-LiS)2Fe2(CO)6. After stirring for 15 min, CF3CO2H (0.016 mL,
0.20 mmol) was added to cause an immediate color change from
green to red, indicating the complete conversion of ( -LiS)2
m
-
Fe2(CO)6 to (m-HS)2Fe2(CO)6. After the mixture was stirred for an
additional 10 min at ꢀ78 ꢁC, 40% aqueous formaldehyde (0.017 mL,
0.20 mmol) was added. The new mixture was allowed to warm to
room temperature and stirred at this temperature for 1 h to give
3.9. X-ray structure determinations of 1e3 and 7
(m-HOCH2S)2Fe2(CO)6. After 6 (0.055 g, 0.08 mmol) was added, the
mixture was stirred at room temperature for 1.5 h. Solvent was
removed in vacuum and the residue was subjected to TLC sepa-
ration using CH2Cl2/petroleum ether (1:1 ¼ v/v) as eluent. From
the purple band, 7 (0.043 g, 51%) was obtained as a purple-red
solid, m.p. 175 ꢁC (dec). Anal. Calcd for C54H37Fe2N5O6S3: C,
61.20; H, 3.52; N, 6.61. Found: C, 60.98; H, 3.78; N, 6.51. IR (KBr
Single crystals of 1e3 and 7 suitable for X-ray diffraction analyses
were grown by slow evaporation of the CH2Cl2/hexane solution of 1
at ꢀ20 ꢁC, as well as by slow diffusion of hexane to the CH2Cl2 so-
lution of 2, slowdiffusion of MeOH tothe o-Cl2C6H4 solution of 3, and
slow diffusion of MeOH to the CH2Cl2 solution of 7 at room tem-
perature, respectively. All the single crystals were mounted on a
Rigaku MM-007 (rotating anode) diffractometer equipped with a
disk): nC
^ 2070 (s), 2027 (vs), 1989 (vs), 1958 (s); npyrrole
O rings
1558 (m), 1473 (s), 1348 (m) cmꢀ1
.
1H NMR (400 MHz, CDCl3):
Saturn 70 CCD. Data were collected at room temperature, using
d
¼ ꢀ2.76 (s, 2H, 2NH of pyrrole rings), 3.10 (t, 2H, J ¼ 6.8 Hz,
ꢀ
a confocal monochromator with MoK
the
a
radiation (
l
¼ 0.71070 A) in
NCH2CH2S), 3.23 (t, 2H, J ¼ 7.0 Hz, NCH2CH2S), 3.76 (s, 4H,
N(CH2S)2), 7.64, 7.66 (2s, 2H, 2o-H of SC6H4), 7.75e7.80 (m, 9H, 6m-
H of 3C6H5, 3p-H of 3C6H5) 8.15, 8.17 (2s, 2H, 2m-H of SC6H4), 8.22,
8.24 (2s, 6H, 6o-H of 3C6H5), 8.80e8.88 (m, 8H, 8CH of pyrrole
rings) ppm. UVevis (CH2Cl2): lmax (log ε) ¼ 418 (4.65), 515 (3.35),
550 (3.07), 591 (2.90), 645 (2.80) nm.
u
ef
scanning mode. Data collection, reduction, and absorption
correction were performed with the CRYSTALCLEAR program [52].
The structures were solved by direct methods using the SHELXS-97
program [53] and refined by full-matrix least-squares techniques
(SHELXL-97) [54] on F2. Hydrogen atoms were located by using the
geometric method. Details of crystal data, data collections, and
structure refinements are summarized in Table 6.
3.8. Preparation of 5-[p-Fe2(CO)5(m-SCH2)2NC2H4SC6H4],10,15,20-
triphenylporphyrin (8)
3.10. Computational methods
To a solution of 7 (0.012 g, 0.011 mmol) in CH2Cl2 was added a
solution of Me3NO$2H2O (0.002 g, 0.018 mmol) in MeCN (5 mL).
After the mixture was stirred at room temperature for 4 h, solvents
were removed and the residue was subjected to TLC separation
using CH2Cl2/petroleum ether (1:1 ¼ v/v) as eluent. From the main
Full geometry optimizations were carried out at the BP86/6-
311þG** level of theory, and the optimized structure was charac-
terized as local minima by frequency analysis at the same level of
theory. All the computations were performed with the Gaussian 09
program [55].

128
L.-C. Song et al. / Journal of Organometallic Chemistry 749 (2014) 120e128
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On the basis of preparing the corresponding precursors1 and 4e6,
we have synthesized the first porphyrinylester moiety- and por-
phyrinylthioether moiety-containing model complexes 2, 3, 7, and 8.
While the porphyrin macrocycle-containing model complex 2 can be
prepared by the porphyrin macrocycle formation reaction of the
simple p-formylbenzoate functionalized model complex 1 with
PhCHO, pyrrole, BF3$OEt2, and p-chloranil, the porphyrinozinc
macrocycle-containing model complex 3 is prepared by coordination
reaction of 2 with Zn(OAc)2. In addition, model complex 7 can be
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prepared by in situ condensation/cyclization reaction of
(m-
HOCH2S)2Fe2(CO)6 with p-aminoethylthio-substituted tetraphe-
nylporphyrin 6, whereas the Me3NO-assisted CO substitution reac-
tion of 7 results in formation of model complex 8. All these new
compounds 1e8 have been characterized by elemental analysis and
various spectroscopic techniques. Particularly noteworthy is that the
X-ray crystallography confirms that 7 has a pendent porphyrinylth-
ioether moiety that is attached to its bridgehead N atom, whereas DFT
computations reveal that the porphyrinylthioether moiety in 8 is
coordinated via its S atom to one Fe atom in its diiron-ADT subsite.
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Acknowledgments
Financial support in China by the State Key Project of Funda-
mental Research for Nanoscience and Nanotechnology (973) (Grant
number 2011CB935902), the National Natural Science Foundation of
China (Grant numbers 21132001, 21272122), Synergetic Innovation
Center of Chemical Science and Engineering (Tianjin), and in USA by
Department of Defense (Grant number W911NF-12-1-0083) and NSF
(Grant number EPS-1010094), is gratefully acknowledged.
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Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jorganchem.2013.09.007.
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