Synthetic and structural studies on linear and macrocyclic Pd- and Pt-bridged butterfly Fe/S cluster complexes

Article abstract of DOI:10.1021/acs.organomet.7b00117

Three types of (diphosphine)Pd- or Pt-bridged butterfly Fe/S cluster complexes have been prepared by a simple and convenient one-pot synthetic method. The first type of such complexes involves the linear (diphosphine)Pd- or Pt-bridged double-butterfly Fe/S clusters [(μ-RS)(μ-S=CS)Fe₂(CO)₆]₂[M-(diphosphine)] (1-12; M = Pd and Pt; R = Et, t-Bu, Ph, and p-MeC₆H₄; diphosphine = dppe, dppv, and dppf), which were prepared by sequential reactions of monoanions [(μ-RS)(μ-CO)-Fe₂(CO)₆]^- (formed in situ from Fe₃(CO)₁₂, RSH, and Et₃N) with excess CS₂, followed by treatment of the resulting monoanions [(μ-RS)(μ-S=CS)Fe₂(CO)₆]^- with (diphosphine)MCl₂. The second type of complexes involves the macrocyclic (diphosphine)M-bridged double-butterfly Fe/S clusters [μ-S(CH₂)₄S-μ][(μ-S=CS)-Fe₂(CO)₆]₂[M(diphosphine)] (13-16; M = Pd and Pt; diphosphine = dppe and dppv), which were prepared by sequential reactions of dianion [{μ-S(CH₂)₄S-μ}{(μ-CO)Fe₂(CO)₆}₂]^2- (generated in situ from Fe₃(CO)₁₂, dithiol HS(CH₂)₄SH, and Et₃N) with excess CS₂, followed by treatment of the resultant dianion [{μ-S(CH₂)₄S-μ}{(μ-S=CS)Fe₂(CO)₆}2]^2- with (diphosphine)MCl₂. In contrast, when dithiol HS(CH₂)₄SH was replaced by HS(CH₂)₃SH (a dithiol with a shorter carbon chain), the aforementioned sequential reactions afforded the third type of macrocyclic complexes which involves the (diphosphine)M-bridged quadruple-butterfly Fe/S clusters [{μ-S(CH₂)₃S-μ}{(μ-S=CS)Fe₂(CO)₆}2]₂[M(diphosphine)]₂ (17-20; M = Pd and Pt; diphosphine = dppe and dppv). While the two possible pathways are suggested for production of the two types of novel macrocyclic Fe/S clusters 13-20, respectively, all new complexes 1-20 have been characterized by elemental analysis, spectroscopy, and, for some of them particularly, DFT calculations and X-ray crystallography.

Full text of DOI:10.1021/acs.organomet.7b00117

Article
pubs.acs.org/Organometallics
Synthetic and Structural Studies on Linear and Macrocyclic Pd- and
Pt-Bridged Butterfly Fe/S Cluster Complexes
,†,‡
†
†
†
†
,†
Li-Cheng Song,*
Long-Duo Zhang, Bei-Bei Liu, Shu-Da Ding, Hao Chen, Xiu-Fang Xu,*
and Gui-Lan Fan†
†
‡
Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry and Collaborative
Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin 300071, China
*
S Supporting Information
ABSTRACT: Three types of (diphosphine)Pd- or Pt-bridged
butterfly Fe/S cluster complexes have been prepared by a simple
and convenient one-pot synthetic method. The first type of such
complexes involves the linear (diphosphine)Pd- or Pt-bridged
double-butterfly Fe/S clusters [(μ-RS)(μ-SCS)Fe (CO) ] [M-
2
6 2
(
diphosphine)] (1−12; M = Pd and Pt; R = Et, t-Bu, Ph, and p-
MeC H ; diphosphine = dppe, dppv, and dppf), which were
6
4
prepared by sequential reactions of monoanions [(μ-RS)(μ-CO)-
−
Fe (CO) ] (formed in situ from Fe (CO) , RSH, and Et N) with
2
6
3
12
3
excess CS , followed by treatment of the resulting monoanions [(μ-
2
−
RS)(μ-SCS)Fe (CO) ] with (diphosphine)MCl . The second
2
6
2
type of complexes involves the macrocyclic (diphosphine)M-bridged
double-butterfly Fe/S clusters [μ-S(CH ) S-μ][(μ-SCS)-
2
4
Fe (CO) ] [M(diphosphine)] (13−16; M = Pd and Pt; diphosphine
2
6 2
2−
=
dppe and dppv), which were prepared by sequential reactions of dianion [{μ-S(CH ) S-μ}{(μ-CO)Fe (CO) } ] (generated
2 4 2 6 2
in situ from Fe (CO) , dithiol HS(CH ) SH, and Et N) with excess CS , followed by treatment of the resultant dianion [{μ-
3
12
2 4
3
2
2−
S(CH ) S-μ}{(μ-SCS)Fe (CO) } ] with (diphosphine)MCl . In contrast, when dithiol HS(CH ) SH was replaced by
2
4
2
6
2
2
2 4
HS(CH ) SH (a dithiol with a shorter carbon chain), the aforementioned sequential reactions afforded the third type of
2
3
macrocyclic complexes which involves the (diphosphine)M-bridged quadruple-butterfly Fe/S clusters [{μ-S(CH ) S-μ}{(μ-S
2
3
CS)Fe (CO) } ] [M(diphosphine)] (17−20; M = Pd and Pt; diphosphine = dppe and dppv). While the two possible pathways
2
6
2 2
2
are suggested for production of the two types of novel macrocyclic Fe/S clusters 13−20, respectively, all new complexes 1−20
have been characterized by elemental analysis, spectroscopy, and, for some of them particularly, DFT calculations and X-ray
crystallography.
INTRODUCTION
butterfly Fe/S complexes, we carried out the sequential
reactions of one-μ-CO-containing monoanions A (formed in
■
The butterfly Fe/S cluster complexes have received great
attention in recent years, largely due to their unique structures
and varied chemical reactivities,
relationship with [FeFe]-hydrogenases.
reported a simple and convenient one-pot synthetic method,
9
,22
situ from Fe (CO) , RSH, and Et N)
and two-μ-CO-
3
12
3
1
−11
containing dianions B and C (generated in situ from
and particularly their close
1
2−20
Fe (CO) , dithiol HS(CH ) SH or HS(CH ) SH, and
3
12
2
4
2 3
In 2010, we
1
0,23
21
Et N)
3
with carbon disulfide and various diphosphine-
chelated Pd or Pt dichlorides. As a result, the expected three
types of the (diphosphine)Pd- or Pt-bridged butterfly Fe/S
complexes were produced. This implies that this one-pot
synthetic method is potentially generalizable for preparation of
the other transition metal-bridged linear and macrocyclic
butterfly Fe/S cluster complexes. Herein, we report the
synthetic procedures and structural characterization of these
novel linear and macrocyclic (diphosphine)Pd- or Pt-bridged
butterfly Fe/S complexes. In addition, the possible pathways for
production of the two types of macrocyclic Fe/S cluster
complexes are also described.
by which three types of (diphosphine)Ni-bridged butterfly Fe/
S complexes were prepared by sequential reactions of the in situ
generated one-μ-CO-containing monoanions [(μ-RS)(μ-CO)-
−
9,22
Fe (CO) ] (A)
and two-μ-CO-containing dianions [{μ-
2
6
2−
10,23
S(CH ) S-μ}{(μ-CO)Fe (CO) } ] (B, n = 4; C, n = 3)
2
n
2
6 2
with carbon disulfide and various diphosphine-chelated nickel
dichlorides. While the first type of such complexes involves a
linear (diphosphine)Ni-bridged double-butterfly Fe/S cluster,
the second and third types of such complexes involve
macrocyclic (diphosphine)Ni-bridged double-butterfly or quad-
ruple-butterfly Fe/S cluster, respectively (Scheme 1).
To show the generality of this one-pot synthetic method and
to prepare the hitherto unknown Pd and Pt analogues of the
previously reported three types of the (diphosphine)Ni-bridged
Received: February 16, 2017
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.organomet.7b00117
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
Scheme 1. Previously Reported (Diphosphine)Ni-Bridged
Butterfly Fe/S Cluster Complexes
Scheme 2. Synthetic Route to Linear Double-Butterfly
Complexes 1−12
21
RESULTS AND DISCUSSION
Synthesis and Structural Characterization of Linear
■
Pd or Pt-Bridged Double-Butterfly Fe/S Clusters [(μ-
RS)(μ-SCS)Fe (CO) ] [M(dppe)] (1, M = Pd, R = Ph; 2,
2
6 2
Pd, Et; 3, Pt, p-MeC H ; 4, Pt, t-Bu), [(μ-RS)(μ-S
6
4
CS)Fe (CO) ] [M(dppv)] (5, M = Pd, R = Ph; 6, Pd, t-Bu;
2
6 2
7
, Pt, p-MeC H ; 8, Pt, t-Bu), and [(μ-RS)(μ-SCS)-
6
4
Fe (CO) ] [M(dppf)] (9, M = Pd, R = Ph; 10, Pd, Et; 11,
2 6 2
Pt, p-MeC H ; 12, Pt, t-Bu). The linear (diphosphine)Pd- or
6
4
Pt-bridged complexes that contain two butterfly [Fe SCS]
2
cluster cores, namely, 1−12, were found to be prepared by
+
sequential reactions of the [Et NH] salts of one-μ-CO-
3
−
containing monoanions [(μ-RS)(μ-CO)Fe (CO) ] (A,
formed in situ from Fe (CO) , Et N, and RSH)
excess CS , followed by treatment of the resulting [Et NH]
While Figures 1 and 2 show their molecular structures, Table 1
gives their selected bond lengths and angles. As shown in
Figure 1, complex 1 indeed consists of two single-butterfly
cluster cores Fe1Fe2S3C13S2 and Fe3Fe4S6C20S5, which are
combined together by the dppe-chelated Pd1 atom through
Pd1−S1 and Pd1−S4 bonds. All 12 CO’s bound to iron atoms
are terminal, and the two phenyl groups are attached to S3 and
S6 atoms via an equatorial type of bonds, C14−S3 (nonbonded
angle ∠C14−S3···S2 = 164.6°) and C21−S6 (nonbonded angle
2
6
9
,22
with
3
12
3
+
2
3
salts of one-μ-CS -containing monoanions [(μ-RS)(μ-S
2
−
24,25
CS)Fe (CO) ] (A′)
with diphosphine dppe-, dppv-, or
2
6
dppf-chelated palladium and platinum dichlorides, respectively
(
Scheme 2).
Linear Pd- or Pt-bridged Fe/S complexes 1−12 are air-stable
red solids and have been characterized by elemental analysis,
infrared (IR) spectrophotometry, and various NMR spectro-
scopic techniques. For example, the IR spectra of 1−12 showed
4
,26
∠C21−S6···S5 = 171.7°).
Thiocarbonyls C13S2 (1.691
Å) and C20S5 (1.684 Å) in complex 1, similar to its Ni
−
1
21
three strong absorption bands in the range of 2061−1975 cm
analogues and the other μ-CS -containing butterfly Fe/S
2
2
7
for their terminal carbonyls and one medium absorption band
complexes, are coordinated to Fe1 and Fe3 by σ-bonds
(Fe1−C13 = 1.966 Å, Fe3−C20 = 1.965 Å) and to Fe2 and
Fe4 through donation of the lone electron pair from S2 or S5
(Fe2−S2 = 2.302 Å, Fe4−S5 = 2.314 Å). As can be seen in
Figure 2, complex 3 is almost isostructural with complex 1. For
example, complex 3 also comprises two single-butterfly cluster
cores (Fe1Fe2S1C20S2 and Fe3Fe4S6C47S5), which are
connected together by the dppe-chelated Pt1 atom via Pt1−
S3 and Pt1−S4 bonds. In addition, its p-MeC H groups are
−1
in the range of 1000−988 cm for their μ-CS groups, which
21
are very close to those corresponding to their Ni analogues,
1
respectively. The H NMR spectra of 3, 7, and 11 showed a
singlet at ca. 2.25 ppm for the methyl groups of their p-MeC H4
6
groups, while those of 4, 6, 8, and 12 displayed a singlet at ca.
1
.42 ppm for the t-Bu groups bound to their bridged S atoms.
31
1
In addition, the P{ H} NMR spectra of 1−8 with organic
diphosphine dppe or dppv ligand exhibited two singlets in the
range of 39−61 ppm attributed to their diphosphine P atoms,
whereas those of 9−12 with organometallic diphosphine dppf
ligand displayed one or two singlets in the region of 12−25
ppm for thier diphosphine P atoms. The C{ H} NMR spectra
of 1−12 displayed a singlet at 308−315 ppm for the C atoms
in their μ-CS groups.
6
4
bound to the bridged S1 and S6 atoms by equatorial type of
bonds, C13−S1 (nonbonded angle ∠C13−S1···S2 = 161.2°)
4
,26
and C48−S6 (nonbonded angle ∠C48−S6···S5 = 162.8°).
1
3
1
Synthesis and Structural Characterization of Macro-
cyclic Pd or Pt-Bridged Double-Butterfly Fe/S Clusters
[μ-S(CH ) S-μ][(μ-SCS)Fe (CO) ] [M(dppe)] (13, M = Pd;
1
3
2
4
2
6 2
To further confirm the molecular structures of representative
linear double-butterfly complexes 1 and 3 and to obtain the
corresponding geometric parameters, the X-ray crystal
diffraction analyses for complexes 1 and 3 were obtained.
14, Pt) and [μ-S(CH ) S-μ][(μ-SCS)Fe (CO) ] [M(dppv)]
2
4
2
6 2
(15, M = Pd; 16, Pt). The macrocyclic (diphosphine)Pd- or
Pt-bridged complexes containing two butterfly [Fe SCS]
2
cluster cores, namely, 13−16, could be prepared by sequential
B
DOI: 10.1021/acs.organomet.7b00117
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
Figure 1. Molecular structure of 1 with 30% probability level ellipsoids. All hydrogen atoms have been omitted for clarity.
2
1
the two μ-CS groups bridged between their two Fe atoms.
31
1
In addition, while the P{ H} NMR spectra of 13−16
exhibited one or two singlets in the range of 40−61 ppm for
1
3
1
the two P atoms in their diphosphine ligands, the C{ H}
NMR spectra of 13−16 displayed a singlet at 312−316 ppm for
the 13C atoms in their μ-CS groups.
To further know the molecular and electronic structures of
the representative macrocycles of Pd- and Pt-bridged
complexes 13 and 14, the DFT calculations on 13 and 14
were carried out. All of the calculations were performed with
28
Gaussian 09 software package. The geometry optimizations
for 13 and 14 were performed in gas phase with the B3LYP
2
9−33
functional.
(
The Stuttgart/Dresden effective core potential
3
4
SDD) was used for iron, palladium, and platinum atoms,
whereas the 6-31G(d) basis set was employed for other atoms.
In addition, the frequency calculations were performed at
2
98.15 K to verify that the two macrocycles were the local
minima.
The DFT-optimized molecular structures of 13 and 14 are
depicted in Figure 3, while Table 2 lists their calculated bond
lengths and angles. As can be seen in Figure 3, complexes 13
and 14 contain two single-butterfly cluster moieties Fe1-
Fe2S5C1S3 and Fe3Fe4S6C2S4 linked together by a butylene
chain (via C3−S5 and C4−S6 bonds) and a dppe-chelated
palladium or platinum moiety (via Pd1−S1 and Pd1−S2 or
Pt1−S1 and Pt1−S2), respectively. The calculated Fe1−Fe2
(2.617 Å) and Fe3−Fe4 (2.618 Å) bond lengths for 13 and 14
are very close to the corresponding bond lengths of their Ni
Figure 2. Molecular structure of 3 with 30% probability level
ellipsoids. All hydrogen atoms have been omitted for clarity.
+
reactions of the [Et NH] salt of two-μ-CO-containing dianion
[
3
2
−
{μ-S(CH ) S-μ}{(μ-CO)Fe (CO) } ] (B, generated in situ
2 4 2 6 2
23
from Fe (CO) , dithiol HS(CH ) SH, and Et N) with excess
3
12
2 4
3
+
CS , followed by treatment of the resultant [Et NH] salt of
2
3
two-μ-CS -containing dianion [{μ-S(CH ) S-μ}{(μ-SCS)-
2
2 4
21
2
−
23
analogues. The butylene group is attached to S5/S6 atoms via
an axial type of bonds C3−S5 (nonbonded angles: ∠C3−S5···
S3 = 77.9° and ∠C4−S6···S4 = 77.2° for 13; ∠C3−S5···S3 =
Fe (CO) } ] (B′) with diphosphine dppe- or dppv-
2
6 2
chelated PdCl and PtCl , respectively (Scheme 3).
2
2
Macrocyclic Pd- or Pt-bridged Fe/S complexes 13−16 are
also air-stable red solids and have been characterized by
elemental analysis and various spectroscopic methods. For
instance, the IR spectra of macrocycles 13−16, similar to those
of linear complexes 1−12, showed three absorption bands in
7
7.8° and ∠C4−S6···S4 = 77.2° for 14) in order to reduce the
ring strains in such a type of microcycles. In addition, the
geometric configurations of the Pd and Pt atoms in 13 and 14
are nearly square-planar, and the bond lengths around Pd1 and
Pt1 atoms are very close to the corresponding bond lengths for
−1
the range of 2053−1975 cm for their terminal CO’s and one
−1
35,36
medium absorption band in the region of 999−989 cm for
other Pd/Pt compounds.
C
DOI: 10.1021/acs.organomet.7b00117
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
Table 1. Selected Bond Lengths (Å) and Angles (deg) for 1 and 3
Complex 1
Pd(1)−P(1)
Pd(1)−P(2)
Pd(1)−S(1)
Pd(1)−S(4)
P(1)−Pd(1)−S(1)
P(1)−Pd(1)−S(4)
P(1)−Pd(1)−P(2)
S(1)−Pd(1)−S(4)
2.2683(10)
2.2655(9)
2.3761(9)
2.3591(10)
94.69(3)
Fe(1)−S(3)
S(2)−C(13)
Fe(2)−S(2)
Fe(1)−Fe(2)
S(2)−Fe(2)−Fe(1)
Fe(2)−S(3)−Fe(1)
Fe(2)−Fe(1)−C(13)
S(3)−Fe(1)−Fe(2)
2.2560(11)
1.691(4)
2.3023(11)
2.6350(8)
74.57(3)
175.91(3)
86.24(4)
71.40(4)
79.56(11)
54.36(3)
89.39(3)
Complex 3
Pt(1)−P(1)
Pt(1)−P(2)
Pt(1)−S(3)
Pt(1)−S(4)
P(1)−Pt(1)−S(4)
P(1)−Pt(1)−S(3)
P(1)−Pt(1)−P(2)
S(3)−Pt(1)−S(4)
2.2599(12)
2.2629(11)
2.3713(11)
2.3684(11)
93.08(4)
Fe(1)−S(1)
Fe(2)−S(1)
Fe(1)−S(2)
Fe(1)−Fe(2)
S(1)−Fe(2)−C(20)
S(1)−Fe(1)−S(2)
S(1)−Fe(1)−Fe(2)
S(2)−Fe(1)−Fe(2)
2.2501(13)
2.2598(14)
2.3039(13)
2.6121(10)
83.74(12)
82.70(5)
172.13(4)
85.98(4)
54.78(4)
87.13(4)
76.00(4)
Scheme 3. Synthetic Route to Macrocyclic Double-Butterfly
Complexes 13−16
Table 2. Selected Bond Lengths (Å) and Angles (deg) for 13
and 14
Complex 13
Pd(1)−P(1)
Pd(1)−P(2)
Pd(1)−S(1)
Pd(1)−S(2)
P(1)−Pd(1)−P(2)
S(1)−Pd(1)−S(2)
P(1)−Pd(1)−S(1)
P(2)−Pd(1)−S(2)
2.357
2.351
2.418
2.410
86.26
91.65
93.00
89.13
Fe(1)−S(3)
Fe(2)−C(1)
Fe(1)−Fe(2)
Fe(3)−Fe(4)
S(5)−Fe(1)−Fe(2)
S(5)−Fe(2)−Fe(1)
S(6)−Fe(3)−Fe(4)
S(6)−Fe(4)−Fe(3)
2.365
2.006
2.617
2.618
55.78
55.35
55.61
55.50
Complex 14
Pt(1)−P(1)
Pt(1)−P(2)
Pt(1)−S(1)
Pt(1)−S(2)
P(1)−Pt(1)−P(2)
S(1)−Pt(1)−S(2)
P(1)−Pt(1)−S(1)
P(2)−Pt(1)−S(2)
2.335
2.331
2.430
2.424
86.73
91.01
92.87
89.40
Fe(1)−S(3)
Fe(2)−C(1)
Fe(1)−Fe(2)
Fe(3)−Fe(4)
S(5)−Fe(1)−Fe(2)
S(5)−Fe(2)−Fe(1)
S(6)−Fe(3)−Fe(4)
S(6)−Fe(4)−Fe(3)
2.365
2.005
2.617
2.618
55.81
55.31
55.63
55.47
The frontier molecular orbitals of 13 and 14 obtained by
DFT calculations are shown in Figure 4. It can be seen that the
highest occupied molecular orbital (HOMO) of 13 is located
Figure 3. Optimized structures of 13 and 14.
D
DOI: 10.1021/acs.organomet.7b00117
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
Scheme 4. Synthetic Route to Macrocyclic Quadruple-
Butterfly Complexes 17−20
Figure 4. Frontier molecular orbitals of 13 and 14 based on DFT
{B3LYP/SDD-6-31G(d)} calculations.
on the two Fe SCS single-butterfly cluster moieties. This
Now, the questions are how were [2 + 2] type macrocycles
17−20 produced from dianion C′, and how were [1 + 1] type
macrocycles 13−16 generated from dianion B′? In order to
answer the two questions, two corresponding possible pathways
are proposed (Scheme 5). As shown in Scheme 5, [1 + 1] type
macrocycles 13−16 are produced first via the intermolecular
nucleophilic attack of the one negatively charged S atom in
2
2
HOMO is mainly characterized by a large Fe−Fe bond density
and is also contributed to by the 3p orbital of S atoms. In
addition, the lowest unoccupied molecular orbital (LUMO) is
located on the PdP S moieties consisting of a Pd center and
2
2
the ligated P and S atoms. This LUMO is mainly characterized
by the d orbital of the Pd atom and the 3p orbital of the ligated
P and S atoms around the Pd center. Similarly, the HOMO of
dianion B′ at Pd or Pt atom in (diphosphine)MCl to give
2
1
4 is also located on the two Fe SCS moieties, and its LUMO
intermediate m and then the intramolecular nucleophilic
2
2
1
is located on the PtP S moieties. It is well-known that the
attack of another negatively charged S atom in m at its Pd or
Pt atom accompanied by ring-closure. However, in contrast to
2
2
1
energy gap between HOMO and LUMO is a characteristic
quantity for the electronic structure of a given molecule. This
quantity is related to the chemical reactivity of a molecule. The
high reactivity of a molecule may be at least partially attributed
to its small energy gap, and the large energy gap may lead to
intermediate m , intermediate m (generated similarly by the
1
2
intermolecular nucleophilic attack of dianion C′ at Pd or Pt
atom of (diphosphine)MCl ) does not easily undergo the
2
intramolecular ring-closure to give the corresponding [1 + 1]
type macrocycles (presumably due to their high strain caused
3
7,38
low reactivity.
3 (3.02 eV) and 14 (3.42 eV) shown in Figure 4 imply that
the chemical reactivity (or stability) of Pd-bridged macrocycle
It follows that the very close energy gaps for
1
by the shorter carbon chain in m ), so [2 + 2] type macrocycles
2
17−20 are finally produced by doubly intermolecular
nucleophilic attacks of the two negatively charged S atoms in
1
3 is very close to that of its Pt analogue 14.
Synthesis and Structural Characterization of Macro-
two molecules of m at their two Pd or Pt atoms, respectively.
2
cyclic Pd or Pt-Bridged Quadruple-Butterfly Fe/S
Clusters [{μ-S(CH ) S-μ}{(μ-SCS)Fe (CO) } ] [M(dppe)]
It is apparent that the proposed pathways shown in Scheme 5
are based on the nucleophilic reactivities of dianions B′/C′, and
the two pathways shown in Scheme 5 are very similar to the
pathways previously suggested for formation of the two types of
2
3
2
6 2 2
2
(
17, M = Pd; 18, Pt) and [{μ-S(CH ) S-μ}{(μ-SCS)-
2
3
Fe (CO) } ] [M(dppv)] (19, M = Pd; 20, Pt). The
2 6 2 2 2
21
macrocyclic (diphosphine)Pd- or Pt-bridged complexes con-
macrocyclic Ni analogues.
taining four butterfly [Fe SCS] cluster cores, namely, 17−20,
Novel [2 + 2] type macrocycles 17−20 (as air-stable red
solids) have been fully characterized by elemental analysis and
various spectroscopic methods. Similar to those of linear
complexes 1−12 and [1 + 1] type macrocycles 13−16, the IR
spectra of 17−20 displayed three strong absorption bands in
2
were found to be prepared by sequential reactions of the
+
[
Et NH] salt of two-μ-CO-containing dianion [{μ-S(CH ) S-
3
2 3
2
−
μ}{(μ-CO)Fe (CO) } ]
Fe (CO) , dithiol HS(CH ) SH, and Et N) with excess
CS and subsequent treatment of the resulting [Et NH] salt of
(C, generated in situ from
2
6 2
21
3
12
2 3
3
+
−1
the range of 2054−1977 cm for their terminal CO’s and one
2
3
−1
the two-μ-CS -containing dianion [{μ-S(CH ) S-μ}{(μ-S
medium absorption band in the region of 999−987 cm for
21
13 1
2
2 3
2−
24
CS)Fe (CO) } ] (C′) with dppe- or dppv-chelated PdCl2
their μ-CS groups. The C{ H} NMR spectra of 17−20
2
6 2
13
or PtCl , respectively (Scheme 4).
showed one singlet at 314−317 ppm for the C atoms in their
2
E
DOI: 10.1021/acs.organomet.7b00117
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
Scheme 5. Two Possible Pathways for Production of the Double-Butterfly Macrocycles 13−16 and Quadruple-Butterfly
Macrocycles 17−20
Figure 5. Whole molecular structure of 17 with 30% probability level ellipsoids. All hydrogen atoms have been omitted for clarity.
3
1
1
4,26
μ-CS groups, whereas their P{ H} NMR spectra exhibited
one singlet in the range of 38−60 ppm for their diphosphine P
atoms. Fortunately, complex 17 as a representative [2 + 2] type
macrocycle was further confirmed by X-ray crystallography.
The whole molecular structure of 17 is depicted in Figure 5,
whereas Figure 6 shows its skeleton structure. In addition,
selected bond lengths and angles are given in Table 3. As can be
seen in Figures 5 and 6, complex 17 contains four single-
butterfly Fe/S clusters Fe1Fe2S9C43S8, Fe3Fe4S4C70S5,
Fe5Fe6S3C86S2, and Fe7Fe8S10C27S12, which are linked by
two propylene chains (via S3/S4 and S9/S10 atoms) and two
dppe-chelated Pd1 and Pd2 atoms (via S6/S7 and S1/S11
atoms) to give a 32-membered metallacycle. It is noteworthy
that the two propylene groups in 17 are attached to S3/S4 and
S9/S10 all by an equatorial type of bonds
(nonbonded
angles: ∠C79−S3···S2 = 162.5°, ∠C77−S4···S5 = 160.3°,
∠C36−S9···S8 = 161.9°, and ∠C34−S10···S12 = 161.2°). In
addition, the eight Fe atoms of 17 all adopt a slightly distorted
square-pyramidal geometry with the average Fe−Fe bond
length of 2.628 Å, whereas its two Pd atoms have a slightly
distorted square-planar geometry with the average Pd−S bond
length of 2.381 Å and Pd−P bond length of 2.276 Å.
21
35,36
SUMMARY AND CONCLUSIONS
■
We have synthesized and characterized the three types of new
(diphosphine)Pd- or Pt-bridged butterfly Fe/S cluster com-
plexes, 1−20. The first type of such complexes, 1−12, are linear
double-butterfly clusters, which can be prepared by sequential
F
DOI: 10.1021/acs.organomet.7b00117
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
Figure 6. Skeleton structure of 17 with 30% probability level ellipsoids.
Table 3. Selected Bond Lengths (Å) and Angles (deg) for 17
Pd(1)−P(11)
Pd(1)−P(14)
Pd(1)−S(6)
Pd(1)−S(7)
S(6)−Pd(1)−S(7)
P(11)−Pd(1)−P(14)
S(7)−Pd(1)−P(11)
Fe(2)−S(8)−C(43)
2.2703(13)
2.2832(14)
2.3919(13)
2.3748(14)
87.03(5)
Fe(1)−S(9)
Fe(2)−S(9)
Fe(2)−S(8)
Fe(1)−Fe(2)
Fe(1)−Fe(2)−S(8)
Fe(2)−Fe(1)−C(43)
S(8)−Fe(2)−S(9)
C(43)−S(8)−Fe(2)
2.089(5)
2.347(3)
2.2900(15)
2.6310(16)
76.04(5)
85.48(5)
77.44(19)
82.89(8)
91.34(5)
93.71(19)
93.71(19)
reactions involving as the final step reaction of monoanions A′
EXPERIMENTAL SECTION
■
with (diphosphine)MCl (M = Pd and Pt). The second type of
2
General Comments. All reactions were carried out using standard
Schlenk and vacuum-line techniques under an atmosphere of nitrogen.
Tetrahedrofuran (THF) was purified by distillation from sodium/
such complexes, 13−16, and third type of such complexes, 17−
2
0, are the two- or four-butterfly Fe/S cluster core-containing
macrocycles, which can be produced by sequential reactions
benzophenone ketyl. RSH (R = Et, t-Bu, Ph, and p-MeC
6 4
H ),
HS(CH ) SH (n = 3 and 4), and (dppe)PdCl (dppe =
involving as the final step reactions of dianions B′ and C′ with
2
n
2
Ph PCH CH PPh ) were available commercially and used as received.
2
2
2
2
(
diphosphine)MCl (M = Pd and Pt), respectively. Based on
2
39
40
Fe (CO) , (dppv)PdCl (dppv = Ph PCHCHPPh ), (dppf)-
3
12
2
2
2
the well-known nucleophilic reactivities of monoanions B′ and
41
42
PdCl2 (dppf = Ph PC H FeC H PPh ), (dppe)PtCl , (dppv)-
2
5
4
5
4
2
2
C′, the two possible pathways for production of [1 + 1] and [2
43
44
PtCl2, and (dppf)PtCl2 were prepared according to literature
procedures. Preparative thin-layer chromatography (TLC) was carried
out on glass plates (26 × 20 × 0.25 cm) coated with silica gel H (10−
+
2] type macrocycles 13−20 are proposed, respectively.
Apparently, the formation of [2 + 2] type macrocycles 17−20
by intermolecular nucleophilic attack between the two
molecules of the propylene (a shorter chain than butylene
present in monoanion m )-bridged monoanion m is in order
4
0 μm). IR spectra were recorded on a Bio-Rad FTS 135 infrared
1
13
1
31
1
spectrophotometer. H, C{ H}, and P{ H} NMR spectra were
obtained on a Bruker Avance 400 NMR spectrometer. Elemental
analyses were performed on an Elementar Vario EL analyzer. Melting
points were determined on a SGW X-4 microscopic melting point
apparatus and were uncorrected.
1
2
to avoid formation of [1 + 1] type high-strain-containing
macrocycles by intramolecular nucleophilic attack of propylene-
bridged monoanion m . While structures of the three types of
Preparation of [(μ-PhS)(μ-SCS)Fe (CO) ] [Pd(dppe)] (1). A
2
2
6 2
complexes 1−20 have been characterized by elemental analysis
and various spectroscopic methods, those of the second type,
complexes 13 and 14, have been further characterized by DFT
calculations, and those of the first and third types, complexes 1,
100 mL three-necked flask equipped with a magnetic stir-bar, a rubber
septum, and a nitrogen inlet tube was charged with PhSH (0.110 mL,
1
.0 mmol), Fe (CO) (0.504 g, 1.0 mmol), Et N (0.140 mL, 1.0
3 12 3
mmol), and THF (15 mL). The mixture was stirred at room
temperature for 0.5 h to give a brown-red solution containing
3, and 17, were confirmed by X-ray crystallography. The
−
monoanion [(μ-PhS)(μ-CO)Fe (CO) ] . The solution was cooled to
2
6
successful synthesis of the three types of Pd- or Pt-bridged
−
40 °C, and then CS (0.120 mL, 2.0 mmol) was added. The new
2
24
−
complexes 1−20 and the corresponding Ni analogues may
mixture containing monoanion [(μ-PhS)(μ-SCS)Fe (CO) ] was
2
6
allow one to expect that such a type of one-pot synthetic
allowed to warm up to room temperature and stirred at this
temperature for 0.5 h. After Pd(dppe)Cl (0.287 g, 0.5 mmol) was
method, which involves unique μ-CS -containing diiron
2
2
added, the new mixture was stirred for 2 h. Solvent was removed at
reduced pressure, and the residue was subjected to TLC separation
using CH Cl /petroleum ether (v/v = 1:2) as eluent. From the main
carbonyl monoanions A′ as well as dianions B′ and C′ as the
novel thiolate-type ligands, might be able to synthesize the
other transition-metal-bridged butterfly Fe/S clusters and thus
be able to promote development of the transition metal cluster
chemistry.
2
2
red band, complex 1 (0.337 g, 47%) was obtained as a red solid, mp
12−113 °C. Anal. Calcd for C H Fe O PdP S : C, 43.53; H, 2.39.
1
52
34
4
12
2 6
Found: C, 43.29; H, 2.54. IR (KBr disk): ν
2056 (vs), 2018 (vs),
CO
G
DOI: 10.1021/acs.organomet.7b00117
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
−
1 1
1
2
979 (vs); ν
992 (m) cm . H NMR (400 MHz, CDCl ): 2.30−
(0.124 g, 1.0 mmol) and (dppv)PtCl (0.331 g, 0.5 mmol) was utilized
CS
3
2
13
1
.39 (m, 4H, CH CH ), 7.15−7.50 (m, 30H, 6C H ) ppm. C{ H}
in place of PhSH and (dppe)PdCl . From the main red band, complex
2
2
6
5
2
NMR (100 MHz, DMSO-d ): 26.8 (s, CH CH ), 126.9−142.9 (m,
7 (0.225 g, 29%) was obtained as a red solid, mp 79−81 °C. Anal.
6
2
2
31
1
C H ), 207.6, 209.1, 211.6 (3s, CO), 311.5 (s, CS) ppm. P{ H}
Calcd for C H Fe O PtP S : C, 41.85; H, 2.34. Found: C, 42.01; H,
6
5
54 36
4
12
2 6
NMR (162 MHz, CDCl , 85% H PO ): 50.7 (s), 51.0 (s) ppm.
2.42. IR (KBr disk): ν
2056 (s), 2018 (vs), 1978 (vs); ν
993
3
3
4
CO
CS
−
1 1
Preparation of [(μ-EtS)(μ-SCS)Fe (CO) ] [Pd(dppe)] (2). The
(m) cm . H NMR (400 MHz, CDCl ): 2.26 (s, 6H, 2CH ), 6.96−
2
6 2
3
3
13 1
same procedure as that for 1 was followed, but EtSH (0.074 mL,1.0
mmol) was used instead of PhSH. From the main red band, complex 2
7.49 (m, 30H, CHCH, 4C H , 2C H ) ppm. C{ H} NMR (100
6
5
6
4
MHz, CDCl ): 21.0 (2s, CH ), 128.8−140.4 (m, C H , C H ), 145.1−
3 3 6 5 6 4
(
0.348 g, 52%) was obtained as a red solid, mp 94−95 °C. Anal. Calcd
for C H Fe O PdP S : C, 39.47; H, 2.56. Found: C, 39.56; H, 2.81.
2052 (vs), 2014 (vs), 1976 (vs); ν
cm . H NMR (400 MHz, DMSO-d ): 1.39 (t, J = 7.2 Hz, 6H,
CH CH ), 2.40−2.69 (m, 8H, 2CH CH , CH CH ), 7.45−7.65 (m,
0H, 4C H ) ppm. C{ H} NMR (100 MHz, DMSO-d ): 18.1 (s,
145.8 (m, CHCH), 208.0, 209.9, 211.7, 212.1 (4s, CO), 314.8 (s,
31
1
CS) ppm. P{ H} NMR (162 MHz, CDCl , 85% H PO ): 48.8
44
34
4
12
2
6
3 3 4
IR (KBr disk): ν
988 (s)
(s), 49.3 (s) ppm.
CO
CS
−1 1
Preparation of [(μ-t-BuS)(μ-SCS)Fe (CO) ] [Pt(dppv)] (8).
6
2
6 2
2
2
The same procedure as that for 1 was followed, but t-BuSH (0.112
2
3
2
3
2
2
13
1
mL, 1.0 mmol) and (dppv)PtCl (0.331 g, 0.5 mmol) were utilized in
6
5
6
2
CH ), 26.8, (s, CH CH ), 34.9 (s, CH CH ), 127.7−132.6 (m, C H ),
place of PhSH and (dppe)PdCl2, respectively. From the main red
band, complex 8 (0.296 g, 40%) was obtained as a red solid, mp 72−
74 °C. Anal. Calcd for C H Fe O PtP S : C, 38.91; H, 2.72. Found:
3
2
2
2
3
6
5
31
1
2
08.0, 210.2, 211.4 (3s, CO), 310.8 (s, CS) ppm. P{ H} NMR
(
162 MHz, CDCl , 85% H PO ): 50.1 (s), 50.6 (s) ppm.
3
3
4
48 40
4
12
2 6
Preparation of [(μ-p-MeC H S)(μ-SCS)Fe (CO) ] [Pt(dppe)]
C, 38.75; H, 2.86. IR (KBr disk): ν
2051 (s), 2014 (vs), 1975 (vs);
6
4
2
6 2
CO
−1 1
(3). The same procedure as that for 1 was followed, but p-MeC H SH
ν
993 (m) cm . H NMR (400 MHz, CDCl ): 1.43 (s, 18H,
6
4
CS
3
(
0.124 g, 1.0 mmol) and (dppe)PtCl (0.332 g, 0.5 mmol) were used
6CH ), 6.88−7.09 (m, 2H, CHCH), 7.47−7.57 (m, 20H, 4C H )
ppm. C{ H} NMR (100 MHz, CDCl ): 34.3 (s, CH ), 49.9 (s,
3 3
2
3
6
5
13
1
instead of PhSH and (dppe)PdCl , respectively. From the main red
2
band, complex 3 (0.287 g, 37%) was obtained as a red solid, mp 75−
C(CH ) ), 129.4−132.1 (m, C H ), 145.1, 145.8 (2s, CHCH),
3
3
6
5
31
1
7
7 °C. Anal. Calcd for C H Fe O PtP S : C, 41.80; H, 2.47. Found:
208.3, 211.7 (2s, CO), 315.1 (s, CS) ppm. P{ H} NMR (162
54
38
4
12
2 6
C, 41.95; H, 2.54. IR (KBr disk): ν
2056 (s), 2018 (vs), 1979 (vs);
MHz, CDCl , 85% H PO ): 48.6 (s), 48.8 (s) ppm.
CO
3
3
4
−1 1
ν
2
7
2
993 (m) cm . H NMR (400 MHz, acetone-d ): 2.25 (s, 6H,
Preparation of [(μ-PhS)(μ-SCS)Fe (CO) ] [Pd(dppf)] (9).
The same procedure as that for 1 was followed, but (dppf)PdCl
2
CS
6
2
6 2
CH ), 2.59−2.68 (m, 4H, CH CH ), 7.01−7.31 (m, 8H, 2C H ),
3
2
2
6
4
13
1
.52−7.70 (m, 20H, 4C H ) ppm. C{ H} NMR (100 MHz, CDCl ):
1.4 (s, CH ), 27.9, 28.3 (2s, CH CH ), 129.1−140.7 (m, C H ,
(0.365 g, 0.5 mmol) was employed instead of (dppe)PdCl . From the
6
5
3
2
3
2
2
6
5
main red band, complex 9 (0.278 g, 35%) was obtained as a red solid,
mp 143 °C (dec). Anal. Calcd for C H Fe O PdP S : C, 45.30; H,
31
1
C H ), 208.3, 210.2, 211.9 (3s, CO), 313.7 (s, CS) ppm. P{ H}
6
4
60 38
5
12
2
6
NMR (162 MHz, CDCl , 85% H PO ): 39.3 (s), 39.7 (s) ppm.
2.41. Found: C, 45.50; H, 2.60. IR (KBr disk): ν
2056 (s), 2018
3
3
4
CO
−
1 1
Preparation of [(μ-t-BuS)(μ-SCS)Fe (CO) ] [Pt(dppe)] (4).
(vs), 1980 (vs); ν
d ): 4.18−4.58 (m, 8H, 2C H ), 7.20−7.64 (m, 30H, 6C H ) ppm.
6
999 (m) cm . H NMR (400 MHz, DMSO-
2
6 2
CS
The same procedure as that for 1 was followed, but t-BuSH (0.112
5
4
6
5
13 1
mL,1.0 mmol) and (dppe)PtCl2 (0.332 g, 0.5 mmol) were used
C{ H} NMR (100 MHz, DMSO-d ): 71.6, 74.1, 75.9 (3s, C H ),
6 5 4
instead of PhSH and (dppe)PdCl , respectively. From the main red
127.0−142.8 (m, C H ), 207.2, 209.1, 211.3 (3s, CO), 308.2 (s,
2
6
5
31
1
band, complex 4 (0.326 g, 44%) was obtained as a red solid, mp 69−
CS) ppm. P{ H} NMR (162 MHz, CDCl , 85% H PO ): 24.2 (s)
3 3 4
7
1 °C. Anal. Calcd for C H Fe O PtP S : C, 38.86; H, 2.85. Found:
ppm.
48
42
4
12
2 6
C, 38.91; H, 2.64. IR (KBr disk): ν
2051 (s), 2014 (vs), 1975 (vs);
Preparation of [(μ-EtS)(μ-SCS)Fe (CO) ] [Pd(dppf)] (10).
CO
2
6 2
−1 1
ν
6
993 (m) cm . H NMR (400 MHz, CDCl ): 1.44 (s, 18H,
The same procedure as that for 1 was followed, but EtSH (0.074
CS
3
CH ), 2.15−2.24 (m, 4H, CH CH ), 7.34−7.68 (m, 20H, 4C H )
mL, 1.0 mmol) and (dppf)PdCl (0.365 g, 0.5 mmol) were used in
3
2
2
6
5
2
13
1
ppm. C{ H} NMR (100 MHz, CDCl ): 27.8, 29.4 (2s, CH CH ),
place of PhSH and (dppe)PdCl , respectively. From the main red
3
2
2
2
3
2
4.5 (s, CH ), 49.8 (s, C(CH ) ), 127.0−134.0 (m, C H ), 208.4,
band, complex 10 (0.314 g, 42%) was obtained as a red solid, mp 137
°C (dec). Anal. Calcd for C H Fe O PdP S : C, 41.78; H, 2.56.
3
3
3
6
5
31
1
11.7, 211.9, 212.3 (4s, CO), 313.8 (s, CS) ppm. P{ H} NMR
52
38
5
12
2
6
(
162 MHz, CDCl , 85% H PO ): 39.1 (s), 39.3 (s) ppm.
Found: C, 41.58; H, 2.47. IR (KBr disk): ν
2052 (vs), 2015 (vs),
3
3
4
CO
−1 1
Preparation of [(μ-PhS)(μ-SCS)Fe (CO) ] [Pd(dppv)] (5).
1976 (vs); ν
993 (m) cm . H NMR (400 MHz, d -DMSO):
2
6 2
CS
6
The same procedure as that for 1 was followed, but (dppv)PdCl2
0.286 g, 0.5 mmol) was utilized in place of (dppe)PdCl . From the
1.37−1.41 (m, 6H, 2CH ), 2.36−2.70 (m, 4H, 2CH ), 4.15−4.19, 4.56
3
2
13 1
(
(m, s, 8H, 2C H ), 7.47−7.65 (m, 20H, 4C H ) ppm. C{ H} NMR
2
5
4
6
5
main red band, complex 5 (0.351 g, 49%) was obtained as a red solid,
(100 MHz, d -DMSO): 18.8 (s, CH ), 35.5 (s, CH ), 74.5, 74.6, 76.3
6 3 2
mp 125−127 °C. Anal. Calcd for C H Fe O PdP S : C, 43.59; H,
(3s, C H ), 129.0−134.2 (m, C H ), 210.8, 211.7, 211.8 (3s, CO),
52
32
4
12
2
6
5
4
6
5
31
1
2
.25. Found: C, 43.55; H, 2.31. IR (KBr disk): ν
2056 (s), 2018
308.5 (s, CS) ppm. P{ H} NMR (162 MHz, CDCl , 85%
CO
3
−1 1
(
vs), 1979 (vs); ν
991 (m) cm . H NMR (400 MHz, DMSO-
H PO ): 23.8 (s), 24.5 (s) ppm.
CS
3
4
d ): 7.19−7.65 (m, 30H, 6C H ), 7.84−8.04 (m, 2H, CHCH) ppm.
Preparation of [(μ-p-MeC H S)(μ-SCS)Fe (CO) ] [Pt(dppf)]
6
6
5
6
4
2
6 2
1
3
1
C{ H} NMR (100 MHz, DMSO-d ): 127.5−133.3 (m, C H ),
(11). The same procedure as that for 1 was followed, but p-
MeC SH (0.124 g, 1.0 mmol) and (dppf)PtCl (0.410 g, 0.5 mmol)
were employed in place of PhSH and (dppe)PdCl , respectively. From
the main red band, complex 11 (0.196 g, 23%) was obtained as a red
solid, mp 118 °C (dec). Anal. Calcd for C62 : C,
43.61; H, 2.48. Found: C, 43.65; H, 2.27. IR (KBr disk): νCO 2061
6
6
5
1
43.4−146.4 (m, CHCH), 208.2, 209.7, 212.2 (3s, CO), 314.0
6
H
4
2
31
1
(
(
s, CS) ppm. P{ H} NMR (162 MHz, CDCl , 85% H PO ): 60.5
2
3
3
4
s), 60.9 (s) ppm.
Preparation of [(μ-t-BuS)(μ-SCS)Fe (CO) ] [Pd(dppv)] (6).
H42Fe O12PtP S
5 2 6
2
6 2
The same procedure was followed as for 1, but t-BuSH (0.112 mL, 1.0
−1 1
mmol) and (dppv)PdCl (0.286 g, 0.5 mmol) were employed in place
(s), 2019 (vs), 1980 (vs); νCS 1000 (m) cm . H NMR (400 MHz,
CDCl ): 2.25 (s, 6H, 2CH ), 4.32 (br.s, 8H, 2C ), 6.96−7.46 (m,
28H, 4C ) ppm. C{ H} NMR (100 MHz, CDCl ): 21.2
(s, CH ), 72.7−76.1 (m, C ), 128.6−140.7 (m, C , C ), 207.7,
209.9, 211.3 (3s, CO), 309.1 (s, CS) ppm. P{ H} NMR (162
MHz, CDCl , 85% H PO ): 12.8 (s) ppm.
Preparation of [(μ-t-BuS)(μ-SCS)Fe
The same procedure as that for 1 was followed, but t-BuSH (0.112
2
of PhSH and (dppe)PdCl , respectively. From the main red band,
3
3
H
5 4
2
13
1
complex 6 (0.348 g, 50%) was obtained as a red solid, mp 99−100 °C.
H
6
5
, 2C
6
H
4
3
Anal. Calcd for C H Fe O PdP S : C, 41.39; H, 2.89. Found: C,
3
5
H
4
6
H
5
H
6 4
48
40
4
12
2
6
31
1
4
ν
6
1.24; H, 3.09. IR (KBr disk): ν
2050 (vs), 2014 (vs), 1975 (vs);
CO
−1 1
990 (m) cm . H NMR (400 MHz, DMSO-d ): 1.40 (s, 18H,
CH ), 7.39−7.69 (m, 20H, 4C H ), 7.75−7.97 (m, 2H, CHCH)
3
3
4
CS
6
(CO) ] [Pt(dppf)] (12).
2 6 2
3
6
5
13
1
ppm. C{ H} NMR (100 MHz, DMSO-d ): 34.1, 34.3 (2s, CH ),
6
3
5
0.1 (s, C(CH ) ), 129.7−133.3 (m, C H ), 145.7−146.4 (m, CH
mL, 1.0 mmol) and (dppf)PtCl
place of PhSH and (dppe)PdCl
2
(0.410 g, 0.5 mmol) were used in
, respectively. From the main red
2
3
3
6
5
31
1
CH), 208.6, 208.9, 212.0 (3s, CO), 314.1 (s, CS) ppm. P{ H}
NMR (162 MHz, CDCl , 85% H PO ): 59.9 (s), 60.1 (s) ppm.
band, complex 12 (0.246 g, 30%) was obtained as a red solid, mp 122
°C (dec). Anal. Calcd for C56 : C, 41.02; H, 2.83.
Found: C, 40.89; H, 2.92. IR (KBr disk): ν 2056 (vs), 2016 (vs),
3
3
4
Preparation of [(μ- p-MeC H S)(μ-SCS)Fe (CO) ] [Pt(dppv)]
7). The same procedure as that for 1 was followed, but p-MeC H SH
6 4
H46Fe O12PtP S
5 2 6
6
4
2
6 2
(
CO
H
DOI: 10.1021/acs.organomet.7b00117
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
−
1 1
1
976 (vs); ν
1000 (m) cm . H NMR (400 MHz, CDCl ): 1.44
Preparation of [{μ-S(CH ) S-μ}{(μ-SCS)Fe (CO) } ] [Pd-
(dppe)] (17). The flask described above was charged with
2
CS
3
2 3
2
6 2 2
(
s, 18H, 6CH ), 4.31 (s, 8H, 2C H ), 7.50 (br.s, 20H, 4C H ) ppm.
C{ H} NMR (100 MHz, CDCl ): 34.5 (s CH ), 49.7 (s, C(CH ) ),
2.9−76.0 (m, C H ), 128.3−134.5 (m, C H ), 208.1, 212.0, 212.1
3s, CO), 310.2 (s, CS) ppm. P{ H} NMR (162 MHz, CDCl ,
3
5
4
6
5
1
3
1
HS(CH ) SH (0.050 mL, 0.5 mmol), Fe (CO) (0.504 g, 1.0
2
3
3
12
3
3
3 3
mmol), Et N (0.140 mL, 1.0 mmol), and THF (15 mL). The mixture
7
(
3
5
4
6
5
31
1
was stirred at room temperature for 0.5 h to give a brown-red solution
3
2
−
containing dianion [{μ-S(CH ) S-μ}{(μ-CO)Fe (CO) } ] . After
8
5% H PO ): 13.3 (s) ppm.
2
3
2
6 2
3
4
the solution was cooled to −40 °C, CS (0.120 mL, 2.0 mmol) was
Preparation of [μ-S(CH ) S-μ][(μ-SCS)Fe (CO) ] [Pd(dppe)]
2
2
4
2
6 2
added. The new mixture containing dianion [{μ-S(CH ) S-μ}{(μ-
(
13). The flask described above was charged with HS(CH ) SH (0.062
2 3
2
4
2
−
SCS)Fe (CO) } ] was allowed to warm up to room temperature
mL, 0.5 mmol), Fe (CO) (0.504 g, 1.0 mmol), Et N (0.140 mL, 1.0
mmol), and THF (15 mL). The mixture was stirred at room
temperature for 0.5 h to give a brown-red solution containing dianion
2
6 2
3
12
3
and stirred at this temperature for 0.5 h. After (dppe)PdCl (0.287 g,
2
0
.5 mmol) was added, the new mixture was stirred for additional 12 h.
2
−
Solvent was removed at reduced pressure, and then the residue was
[
−
{μ-S(CH ) S-μ}{(μ-CO)Fe (CO) } ] . The solution was cooled to
2 4 2 6 2
subjected to TLC using CH Cl /petroleum ether (v/v = 1:1) as
40 °C, and then CS (0.120 mL, 2.0 mmol) was added. The new
2
2
2
eluent. From the main red band, complex 17 (0.077 g, 12%) was
obtained as a red solid, mp 118−119 °C. Anal. Calcd for
C H Fe O Pd P S : C, 39.04; H, 2.29. Found: C, 39.22; H, 2.41.
mixture containing dianion [{μ-S(CH ) S-μ}{(μ-SCS)-
2
4
2−
Fe (CO) } ] was allowed to warm up to room temperature and
2
6 2
86
60
8
24
2 4 12
stirred at this temperature for 0.5 h. After Pd(dppe)Cl (0.287 g, 0.5
2
IR (KBr disk): ν
2052 (vs), 2013 (vs), 1978 (vs); ν
987 (m)
CO
CS
mmol) was added, the new mixture was stirred for additional 12 h.
Solvent was removed at reduced pressure, and the residue was
subjected to TLC using CH Cl /petroleum ether (v/v = 1:1) as
−
1
1
cm
.
H NMR (400 MHz, CD Cl ): 2.11−2.66 (m, 20H,
2
2
2
PCH CH P, 2SCH CH CH S), 7.24−7.54 (m, 40H, 8C H ) ppm.
2
2
2
2
2
6
5
2
2
13
1
C{ H} NMR (100 MHz, CD Cl ): 27.0 (s, PCH CH P), 36.6 (s,
2
2
2
2
eluent. From the main red band, complex 13 (0.071 g, 11%) was
obtained as a red solid, mp 121−122 °C. Anal. Calcd for
C H Fe O PdP S : C, 39.53; H, 2.41. Found: C, 39.52; H, 2.54.
SCH CH CH S), 41.3 (s, SCH CH CH S), 128.3−133.5 (m, C H ),
2
2
2
2
2
2
6
5
3
1
1
2
08.1, 210.4, 211.7, 212.5 (4s, CO), 314.7 (s, CS) ppm. P{ H}
4
4
32
4
12
2 6
NMR (162 MHz, CDCl , 85% H PO ): 49.9 (s) ppm.
3
3
4
IR (KBr disk): ν
2052 (s), 2014 (s), 1975 (vs); ν
990 (s)
CO
CS
−1
1
Preparation of [{μ-S(CH
2
)
3
S-μ}{(μ-SCS)Fe
dppe)] (18). The same procedure as that for 17 was followed, but
2
2 6 2 2
(CO) } ] [Pt-
cm . H NMR (400 MHz, CDCl ): 2.08−2.63 (m, 12H, PCH CH P,
3
2
2
(
1
3
1
SCH CH CH CH S), 7.26−7.65 (m, 20H, 4C H ) ppm. C{ H}
2
2
2
2
6
5
(
(
dppe)PtCl (0.332 g, 0.5 mmol) was used in place of (dppe)PdCl
2
2
NMR (100 MHz, CDCl ): 27.4, 29.8 (2s, PCH CH P), 32.3, 41.0 (2s,
3
2
2
note that after Pt(dppe)Cl was added the new mixture was stirred
2
SCH CH CH CH S), 129.3−133.9 (m, C H ), 208.2, 210.3, 212.0,
2
2
2
2
6
5
for 24 h). From the main red band, complex 18 (0.073 g, 10%) was
obtained as a red solid, mp 105 °C (dec). Anal. Calcd for
C H Fe O Pt P S : C, 36.59; H, 2.14. Found: C, 36.80; H, 2.35.
3
1
1
2
12.5 (4s, CO), 313.8 (s, CS) ppm. P{ H} NMR (162 MHz,
CDCl , 85% H PO ): 51.3 (s) ppm.
3
3
4
86
60
8
24
2 4 12
Preparation of [μ-S(CH ) S-μ][(μ-SCS)Fe (CO) ] [Pt(dppe)]
2
4
2
6 2
IR (KBr disk): ν
2053 (vs), 2014 (vs), 1977 (vs); ν
999 (m)
CO
CS
(
14). The same procedure as that for 13 was followed, but
−1
1
cm
.
H NMR (400 MHz, CDCl ): 1.88−2.69 (m, 20H,
3
Pt(dppe)Cl (0.332 g, 0.5 mmol) was used instead of Pd(dppe)Cl2
note that after Pt(dppe)Cl was added the new mixture was stirred
for 24 h). From the main red band, complex 14 (0.069 g, 10%) was
obtained as a red solid, mp 110 °C (dec). Anal. Calcd for
C H Fe O PtP S : C, 37.07; H, 2.26. Found: C, 37.12; H, 2.46.
2
2
PCH CH P, 2SCH CH CH S), 7.28−7.66 (m, 40H, 8C H ) ppm.
2
2
2
2
2
6
5
(
13
1
2
C{ H} NMR (100 MHz, CDCl ): 29.7 (s, PCH CH P), 36.2 (s,
3
2
2
SCH CH CH S), 41.3 (s, SCH CH CH S), 128.9−133.9 (m, C H ),
2
2
2
2
2
2
6
5
31
1
2
07.9, 210.6, 211.6, 212.1 (4s, CO), 314.8 (s, CS) ppm. P{ H}
4
4
32
4
12
2 6
NMR (162 MHz, CDCl , 85% H PO ): 38.1 (s) ppm.
3
3
4
IR (KBr disk): ν
2052 (s), 2016 (vs), 1976 (vs); ν
999 (m)
CO
CS
Preparation of [{μ-S(CH ) S-μ}{(μ-SCS)Fe (CO) } ] [Pd-
−1
1
2 3
2
6 2 2
cm . H NMR (400 MHz, CDCl ): 2.03−2.68 (m, 12H, PCH CH P,
3
2
2
(dppv)] (19). The same procedure as that for 17 was followed, but
2
1
3
1
SCH CH CH CH S), 7.29−7.68 (m, 20H, 4C H ) ppm. C{ H}
2
2
2
2
6
5
(dppv)PdCl (0.286 g, 0.5 mmol) was used instead of (dppe)PdCl .
2
2
NMR (100 MHz, CDCl ): 28.4, 29.7 (2s, PCH CH P), 32.1, 40.7 (2s,
3
2
2
From the main red band, complex 19 (0.061 g, 9%) was obtained as a
red solid, mp 122−124 °C. Anal. Calcd for C H Fe O Pd P S : C,
SCH CH CH CH S), 126.8−133.7 (m, C H ), 208.0, 210.6, 211.6,
2
2
2
2
6
5
86
56
8
24
2 4 12
3
1
1
2
12.1 (4s, CO), 312.7 (s, CS) ppm. P{ H} NMR (162 MHz,
3
9.10; H, 2.14. Found: C, 39.00; H, 2.27. IR (KBr disk): ν
2053
CO
−1 1
CDCl , 85% H PO ): 40.4 (s), 40.7 (s) ppm.
3
3
4
(s), 2014 (vs), 1978 (vs); ν
987 (m) cm . H NMR (400 MHz,
CS
Preparation of [μ-S(CH ) S-μ][(μ-SCS)Fe (CO) ] [Pd(dppv)]
2
4
2
6 2
CD Cl ): 2.19−2.37 (m, 4H, 2SCH CH CH S), 2.65−2.76 (m, 8H,
2
2
2
2
2
(
(
15). The same procedure as that for 13 was followed, but
2
SCH CH CH S), 7.12−7.61 (m, 44H, 2CHCH, 8C H ) ppm.
C{ H} NMR (100 MHz, CD Cl ): 36.8 (s, SCH CH CH S), 41.5
2 2 2 2 2
2
2
2
6
5
dppv)PdCl (0.286 g, 0.5 mmol) was used instead of Pd(dppe)Cl .
13
1
2
2
From the main red band, complex 15 (0.073 g, 11%) was obtained as a
red solid, mp 118−119 °C. Anal. Calcd for C H Fe O PdP S : C,
9.59; H, 2.27. Found: C, 39.73; H, 2.42. IR (KBr disk): ν
(
s, SCH CH CH S), 129.6−133.5 (s, C H ), 145.1−145.9 (m, CH
2
2
2
6
5
44
30
4
12
2
6
CH), 208.4, 210.7, 211.8, 213.0 (4s, CO), 316.7 (s, CS) ppm.
P{ H} NMR (162 MHz, CDCl , 85% H PO ): 59.8 (s) ppm.
3 3 4
3
2052
31
1
CO
−1 1
(
s), 2014 (s), 1976 (vs); ν
989 (s) cm . H NMR (400 MHz,
CS
Preparation of [{μ-S(CH ) S-μ}{(μ-SCS)Fe (CO) } ] [Pt-
2
3
2
6 2 2
CDCl ): 2.02−2.84 (m, 8H, CH CH CH CH ), 7.00−7.53 (m, 22H,
3
2
2
2
2
(dppv)] (20). The same procedure as that for 17 was followed, but
2
13
1
CHCH, 4C H ) ppm. C{ H} NMR (100 MHz, CDCl ): 32.3,
6
5
3
(dppv)PtCl (0.331 g, 0.5 mmol) was used in place of (dppe)PdCl
2
2
4
2
0.9 (2s, CH ), 129.6−133.7 (m, C H ), 144.9−145.7 (m, CHCH),
2
6
5
(note that after Pt(dppv)Cl was added the new mixture was stirred
2
31
1
08.1, 210.3, 211.8, 213.0 (4s, CO), 315.5 (s, CS) ppm. P{ H}
for 24 h). From the main red band, complex 20 (0.066 g, 9%) was
obtained as a red solid, mp 112 °C (dec). Anal. Calcd for
NMR (162 MHz, CDCl , 85% H PO ): 60.5, 60.7 (2s) ppm.
3
3
4
Preparation of [μ-S(CH ) S-μ][(μ-SCS)Fe (CO) ] [Pt(dppv)]
2
4
2
6 2
C
86
H
56Fe
8
O
24Pt
2
P
CO
4
S
12: C, 36.64; H, 2.00. Found: C, 36.57; H, 2.14.
2054 (s), 2015 (vs), 1977 (vs); ν 999 (m)
(
16). The same procedure as that for 13 was followed, but
IR (KBr disk): ν
cm
CS
Pt(dppv)Cl (0.331 g, 0.5 mmol) was used instead of Pd(dppe)Cl2
note that after Pt(dppv)Cl was added the new mixture was stirred
2
for 24 h). From the main red band, complex 16 (0.088 g, 12%) was
obtained as a red solid, mp 104 °C (dec). Anal. Calcd for
C H Fe O PtP S : C, 37.12; H, 2.12. Found: C, 37.09; H, 2.22.
−1
1
2
.
H NMR (400 MHz, CDCl ): 2.00−2.80 (m, 12H,
3
(
2CH CH CH ), 6.89−7.55 (m, 44H, 2CHCH, 8C H ) ppm.
2
2
2
6
5
13
1
C{ H} NMR (100 MHz, CDCl ): 36.3 (s, SCH CH CH S), 41.4
3
2
2
2
(
s, SCH CH CH S), 126.9−133.6 (m, C H ), 145.3−145.9 (m, CH
2
2
2
6
5
31
1
4
4
30
4
12
2
6
CH), 208.0−212.7 (m, CO), 316.6 (s, CS) ppm. P{ H} NMR
IR (KBr disk): ν
cm
2053 (s), 2016 (vs), 1976 (vs); ν
991 (m)
CO
CS
(162 MHz, CDCl , 85% H PO ): 47.9 (s) ppm.
3
3
4
−
1
1
.
H NMR (400 MHz, CDCl ): 1.89−2.64 (m, 8H,
3
X-ray Structure Determinations of 1, 3, and 17. While single
crystals of 1 and 3 suitable for X-ray diffraction analysis were grown by
slow diffusion of hexane into their CH Cl solutions at −35 °C and −5
CH CH CH CH ), 6.96−7.46 (m, 22H, CHCH, 4C H ) ppm.
2
2
2
2
6
5
1
3
1
C{ H} NMR (100 MHz, CDCl ): 32.6, 40.7 (2s, CH ), 126.8−133.5
3
2
2
2
(
3
m, C H ), 145.2−145.8 (m, CHCH), 208.0−212.6 (m, CO),
°C, respectively, those of 17 suitable for X-ray diffraction analysis were
grown by slow diffusion of diethyl ether into its CH Cl solution at
6
5
31
1
14.3 (s, CS) ppm. P{ H} NMR (162 MHz, CDCl , 85%
3
2
2
H PO ): 48.7 (s) ppm.
−35 °C. A single crystal of 1 or 3 was mounted on a Rigaku MM-007
3
4
I
DOI: 10.1021/acs.organomet.7b00117
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
Table 4. Crystal Data and Structure Refinements Details for 1, 3, and 17
1
3
17
mol formula
mol wt
cryst syst
space group
a (Å)
C H Fe O P PdS
C H Fe O P PtS
C H Fe O P Pd S
5
2
34
4
12
2
6
54 38
4
12
2
6
86 60
8
24
4
2
12
1434.89
1551.63
2645.54
monoclinic
C2/c
monoclinic
P21/n
14.633(4)
23.032(5)
22.401(5)
90
monoclinic
P21/c
35.363(3)
15.3709(3)
34.0985(7)
25.7071(5)
90
b (Å)
14.7490(13)
27.309(2)
90
c (Å)
α (deg)
β (deg)
γ (deg)
V (Å3)
Z
124.423(2)
90
108.993(5)
90
100.151(2)
90
11749.3(18)
8
7139(3)
4
13262.8(5)
4
D (g·cm−3)
1.622
1.444
1.325
c
abs coeff (mm−1)
1.589
3.015
1.402
F(000)
5744
3064
5280
−
46 ≤ h ≤ 44
−19 ≤ k ≤ 19
35 ≤ l ≤ 35
−17 ≤ h ≤ 17
−27 ≤ k ≤ 27
−26 ≤ l ≤ 22
59960
−19 ≤ h ≤ 18
−42 ≤ k ≤ 40
−32 ≤ l ≤ 31
68285
index ranges
−
53730
no. of reflns
no. of indep reflns
14038
12579
27078
2
θmax (deg)
55.88
50.02
52.74
R
0.0535
0.1004
1.135
0.0361
0.0659
Rw
0.0952
0.1794
GOF
1.049
1.100
largest diff peak, hole (e Å−3)
0.520/−0.805
1.763/−1.259
2.627/−3.007
(
rotating anode) diffractometer equipped with a Saturn 724 CCD, and
ACKNOWLEDGMENTS
■
data were collected using a confocal monochromator with Mo Kα
radiation (λ = 0.71075 or λ = 0.71073 Å) in the ω scanning mode at
1
diffractometer equipped with an Eos, and data were collected using a
confocal monochromator with Mo Kα radiation (λ = 0.7107 Å) in the
ω scanning mode at 99.9 K. Data collection, reduction, and absorption
correction were performed by CRYSTALCLEAR program. The
structures were solved by direct methods using the SHELXS-97
We are grateful to the Ministry of Science and Technology of
China (973 program 2014CB845604) and the National Natural
Science Foundation of China (21472095, 21421001) for
financial support.
13 K. A single crystal of 17 was mounted on a SuperNova
4
5
REFERENCES
■
4
6
program and refined by full-matrix least-squares techniques
(1) For reviews, see for example (a) Marko,
́
L.; Marko-
́
Monostory, B.
47
2
(
SHELXL-97) on F . Hydrogen atoms were located by using the
In The Organic Chemistry of Iron; von Gustor, E. A. K., Grevels, F. W.,
Fischler, I., Eds.; Academic Press: New York, 1981; Vol. 2, p. 283.
(b) Song, L.-C. Trends Organomet. Chem. 1999, 3, 1−20. (c) Song, L.-
C. Acc. Chem. Res. 2005, 38, 21−28. (d) Song, L.-C. Sci. China, Ser. B:
Chem. 2009, 52, 1−14. (e) Li, Y.; Rauchfuss, T. B. Chem. Rev. 2016,
geometric method. Details of crystal data, data collections, and
structure refinements are summarized in Table 4.
ASSOCIATED CONTENT
■
1
(
16, 7043−7077.
*
S
Supporting Information
2) Nametkin, N. S.; Tyurin, V. D.; Kukina, M. A. J. Organomet.
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.organo-
met.7b00117.
Chem. 1978, 149, 355−370.
(3) Seyferth, D.; Song, L.-C.; Henderson, R. S. J. Am. Chem. Soc.
1981, 103, 5103−5107.
(
1
(
4) Seyferth, D.; Henderson, R. S.; Song, L.-C. Organometallics 1982,
IR and NMR spectra of the representative complexes 2,
, 125−133.
5) Winter, A.; Zsolnai, L.; Huttner, G. Z. Naturforsch., B: J. Chem.
Sci. 1982, 37, 1430−1436.
6) Bose, K. S.; Sinn, E.; Averill, B. A. Organometallics 1984, 3, 1126−
128.
7) Kovacs, J. A.; Bashkin, J. K.; Holm, R. H. J. Am. Chem. Soc. 1985,
07, 1784−1786.
(8) Mathur, P.; Ghosh, S.; Sarkar, A.; Satyanarayana, C. V. V;
Puranik, V. G. Organometallics 1997, 16, 4392−4398.
9) Seyferth, D.; Womack, G. B.; Dewan, J. C. Organometallics 1985,
, 398−400.
10) Song, L.-C.; Fan, H.-T.; Hu, Q.-M. J. Am. Chem. Soc. 2002, 124,
566−4567.
11) Song, L.-C.; Tan, H.; Zhu, A.-G.; Hu, Y.-Y.; Chen, H.
Organometallics 2015, 34, 1730−1741.
12) For reviews, see for example (a) Simmons, T. R.; Berggren, G.;
8, 11, 13, and 20 (PDF)
Crystal data, atomic coordinates, and thermal parameters,
and bond lengths and angles for 1, 3, and 17 (CIF)
Cartesian coordinates of 13 and 14 (XYZ)
(
1
(
1
AUTHOR INFORMATION
■
Corresponding Authors
(
4
(
4
*
*
E-mail: lcsong@nankai.edu.cn
E-mail: xxfang@nankai.edu.cn.
ORCID
(
Li-Cheng Song: 0000-0003-0964-8869
Notes
(
The authors declare no competing financial interest.
Bacchi, M.; Fontecave, M.; Artero, V. Coord. Chem. Rev. 2014, 270−
J
DOI: 10.1021/acs.organomet.7b00117
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
2
71, 127−150. (b) Lubitz, W.; Ogata, H.; Ru
̈
diger, O.; Reijerse, E.
(37) Begum, P.; Bhattacharjee, D.; Mishra, B. K.; Deka, R. C. Theor.
Chem. Acc. 2014, 133, 1418−1428.
Chem. Rev. 2014, 114, 4081−4148. (c) Schilter, D.; Camara, J. M.;
Huynh, M.; Hammes-Schiffer, S.; Rauchfuss, T. B. Chem. Rev. 2016,
(38) Saleem, F.; Rao, G. K.; Kumar, A.; Kumar, S.; Singh, M. P.;
Singh, A. K. RSC Adv. 2014, 4, 56102−56111.
(39) King, R. B. Organometallic Syntheses: Transiton Metal
Compounds; Academic Press: New York, 1965; Vol. 1, p 95.
(40) Chow, K. K.; Levason, W.; McAuliffe, C. A. Inorg. Chim. Acta
1975, 15, 79−83.
1
16, 8693−8749.
13) Lawrence, J. D.; Li, H.; Rauchfuss, T. B.; Ben
M.-M. Angew. Chem., Int. Ed. 2001, 40, 1768−1771.
14) George, S. J.; Cui, Z.; Razavet, M.; Pickett, C. J. Chem. - Eur. J.
002, 8, 4037−4046.
15) Chong, D.; Georgakaki, I. P.; Mejia-Rodriguez, R.; Sanabria-
Chinchilla, J.; Soriaga, M. P.; Darensbourg, M. Y. Dalton Trans. 2003,
158−4163.
16) Song, L.-C.; Tang, M.-Y.; Su, F.-H.; Hu, Q.-M. Angew. Chem.,
Int. Ed. 2006, 45, 1130−1133.
17) Song, L.-C.; Wang, Y.-X.; Xing, X.-K.; Ding, S.-D.; Zhang, L.-D.;
Wang, X.-Y.; Zhang, H.-T. Chem. - Eur. J. 2016, 22, 16304−16314.
18) Manor, B. C.; Ringenberg, M. R.; Rauchfuss, T. B. Inorg. Chem.
014, 53, 7241−7247.
19) Menzel, K.; Apfel, U.-P.; Wolter, N.; Ru
Steiniger, F.; Gabel, D.; Forster, S.; Weigand, W.; Fahr, A. J. Liposome
Res. 2014, 24, 59−68.
20) Berggren, G.; Adamska, A.; Lambertz, C.; Simmons, T. R.;
(
́
ard, M.; Rohmer,
(
2
(
(41) Nataro, C.; Fosbenner, S. M. J. Chem. Educ. 2009, 86, 1412−
1415.
(42) Rauchfuss, T. B.; Shu, J. S.; Roundhill, D. M. Inorg. Chem. 1976,
15, 2096−2101.
(43) Michelin, R. A.; Facchin, G.; Braga, D.; Sabatino, P.
Organometallics 1986, 5, 2265−2274.
(44) Colacot, T. J.; Qian, H.; Cea-Olivares, R.; Hernandez-Ortega, S.
J. Organomet. Chem. 2001, 637−639, 691−697.
(45) CrystalClear and CrystalStructure; Rigaku and Rigaku Americas:
The Woodlands, TX, 2007.
4
(
(
(
2
(
̈
ger, R.; Alpermann, T.;
(
46) Sheldrick, G. M. SHELXS97, A Program for Crystal Structure
Solution; University of Gottingen: Gottingen, Germany, 1997.
47) Sheldrick, G. M. SHELXL97, A Program for Crystal Structure
̈
̈
̈
(
(
Refinement; University of Go
̈
ttingen: Go
̈
ttingen, Germany, 1997.
Esselborn, J.; Atta, M.; Gambarelli, S.; Mouesca, J.-M.; Reijerse, E.;
Lubitz, W.; Happe, T.; Artero, V.; Fontecave, M. Nature 2013, 499,
6
(
2
(
6−69.
21) Song, L.-C.; Li, Y.-L; Li, L.; Gu, Z.-C.; Hu, Q.-M. Inorg. Chem.
010, 49, 10174−10182.
22) Song, L.-C.; Yan, C.-G.; Hu, Q.-M.; Wang, R.-J.; Mak, T. C. W.;
Huang, X.-Y. Organometallics 1996, 15, 1535−1544.
23) Song, L.-C.; Fan, H.-T.; Hu, Q.-M.; Yang, Z.-Y.; Sun, Y.; Gong,
F.-H. Chem. - Eur. J. 2003, 9, 170−180.
24) Seyferth, D.; Womack, G. B.; Archer, C. M.; Fackler, J. P., Jr.;
Marler, D. O. Organometallics 1989, 8, 443−450.
25) Song, L.-C.; Yan, C.-G.; Hu, Q.-M.; Wu, B.-M.; Mak, T. C. W.
Organometallics 1997, 16, 632−635.
26) Shaver, A.; Fitzpatrick, P. J.; Steliou, K.; Butler, I. S. J. Am. Chem.
Soc. 1979, 101, 1313−1315.
27) Patin, H.; Mignani, G.; Mahe,
T. G.; Benoit, A.; Grandjean, D. J. Organomet. Chem. 1980, 197, 315−
25.
28) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
(
(
(
(
(
́
C.; Le Marouille, J.-Y.; Southern,
3
(
Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci,
B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H.
P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.;
Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima,
T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A., Jr.;
Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin,
K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.;
Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega,
N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.;
Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.;
Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.;
Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.;
Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.;
Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09,
revision E.01; Gaussian, Inc.: Wallingford, CT, 2009.
(
3
(
29) Becke, A. D. Phys. Rev. A: At., Mol., Opt. Phys. 1988, 38, 3098−
100.
30) Lee, C.; Yang, W. T.; Parr, R. G. Phys. Rev. B: Condens. Matter
Mater. Phys. 1988, 37, 785−789.
(31) Becke, A. D. J. Chem. Phys. 1993, 98, 5648−5652.
(32) Becke, A. D. J. Chem. Phys. 1993, 98, 1372−1377.
(33) Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.; Frisch, M. J. J.
Phys. Chem. 1994, 98, 11623−11627.
34) Andrae, D.; Hauβermann, U.; Dolg, M.; Stoll, H.; Preuβ, H.
Theor. Chim. Acta 1990, 77, 123−141.
35) Arumugam, K.; Shaw, M. C.; Mague, J. T.; Bill, E.; Sproules, S.;
Donahue, J. P. Inorg. Chem. 2011, 50, 2995−3002.
36) Hirano, M.; Tatesawa, S.; Yabukami, M.; Ishihara, Y.; Hara, Y.;
Komine, N.; Komiya, S. Organometallics 2011, 30, 5110−5112.
(
̈
(
(
K
DOI: 10.1021/acs.organomet.7b00117
Organometallics XXXX, XXX, XXX−XXX