Synthesis of a New Family of Heteronuclear Thiolate Iron Complexes that Contain Isocyanide Ligands

Article abstract of DOI:10.1002/ejic.201000676

Treatment of complex [Cp*Fe(I-SEt)₃FeCp*] (1; Cp* = pentamethylcyclopentadienyl) with isocyanides CNR affords the mononuclear complexes [Cp*FeSEt(CNR)₂] (2a, R = tBu; 2b, R = Ph; 2c, R = Cy; 2d, R = Bn) in moderate yield. The heterob

Full text of DOI:10.1002/ejic.201000676

FULL PAPER
DOI: 10.1002/ejic.201000676
Synthesis of a New Family of Heteronuclear Thiolate Iron Complexes that
Contain Isocyanide Ligands
Pingping Chen,[a] Ying Peng,[a] Chunmei Jia,[a] and Jingping Qu*[a]
Keywords: Transition metals / Heteronuclear complexes / Isocyanide ligands / Thiolate ligands
Treatment of complex [Cp*Fe(µ-SEt)3FeCp*] (1; Cp*
=
nuclear complexes [{Cp*Fe(CNtBu)2(µ-SEt)}2M][PF6] (5, M =
Au; 6, M = Ag; 7, M = Cu) have been prepared by the reac-
tion of 2 with complexes [PdCl2(PPh3)2], [NiCl2(PPh3)2], and
[(Ph3P)M][X] (X = PF6 or OTf, OTf = OSO2CF3), respectively.
These complexes have been spectroscopically and crystallo-
graphically characterized.
pentamethylcyclopentadienyl) with isocyanides CNR affords
the mononuclear complexes [Cp*FeSEt(CNR)2] (2a, R = tBu;
2b, R = Ph; 2c, R = Cy; 2d, R = Bn) in moderate yield. The
heterobinuclear complexes [Cp*FeCNR(µ-CNR)(µ-SEt)PdCl-
(PPh3)][PF6] (3a, R = tBu; 3b, R = Ph; 3c, R = Cy; 3d, R = Bn),
[Cp*Fe(CNtBu)2(µ-SEt)NiCl(PPh3)][PF6] (4), and heterotri-
deal and these complexes show some unique properties.[7]
In our previous work, we reported thiolate-bridged diiron
complexes that contain isocyanide ligands with excellent
properties for the activation of C–Cl of some chlorohydro-
carbons,[8] whereas the heterobinuclear isocyanide-bridged
complexes that contain iron atoms have scarcely been re-
ported, and the only example is [(CO)3Fe(µ-CNR)(µ-
dppm)Pt(PPh3)] (R = 2,6-xylyl or o-anisyl).[9] Additionally,
complexes that contain noble metals can be used as cata-
lysts in various kinds of organic transformations such as C–
C bond-forming reactions.[10] These findings prompted us
to synthesize new heteronuclear thiolate iron complexes
with noble metals that contain isocyanide ligands, which
might show some unique properties. Herein we report our
preliminary results on the preparation of heterobinuclear
Fe–SEt–M (M = Pd or Ni) complexes and heterotrinuclear
Fe–SEt–M–SEt–Fe (M = Au, Ag, or Cu) complexes and
their spectroscopic and crystallographic characterizations.
Introduction
Heteronuclear complexes are of broad interest due to the
differences these systems have in their bonding and reacti-
vity versus homonuclear species.[1] With two or more dispa-
rate metal centers in a single molecule, the potential exists
for cooperative behavior that can improve the selectivity
and efficiency of catalyzation and can promote reactions
that are not possible using a single metal center.[2] Iron–
sulfur complexes have received increasing attention on ac-
count of their unusual structures and occurrence in bio-
logical metalloproteins including nitrogenase, hydrogenase,
and ferredoxins.[3] Acting as the active sites in numerous
proteins in various organisms, they usually serve as elec-
tron-transport functionalities and complete biological reac-
tions through cooperative actions of many metal centers in
the form of clusters.[4] The chemistry of heteronuclear iron
complexes with group 10 (Ni, Pd, and Pt)[5] and 11 (Au,
Ag, and Cu)[6] metals have been extensively studied for the
catalytic activity and application in material science, and
these complexes are mainly stabilized by bridging neutral
ligands (such as CO and phosphane ligands) or sulfide li-
gands. However, the thiolate-bridged heterobinuclear or
heterotrinuclear complexes, especially those that contain Au
and Ag atoms, have rarely been investigated.
Results and Discussion
Synthesis and Characterization of [Cp*FeSEt(CNR)2] (2a,
R = tBu; 2b, R = Ph; 2c, R = Cy; 2d, R = Bn)
Treatment of the binuclear complex [Cp*Fe(µ-SEt)3-
FeCp*] (1; Cp* = pentamethylcyclopentadienyl) with CNR
(5 equiv.) in THF at room temperature for 12 h afforded
mononuclear complex [Cp*FeSEt(CNR)2] (2) as a brown-
red solid in moderate yield (Scheme 1). Several isocyanides
with different R substituents were used, and all of the re-
sulting complexes were found to be air-sensitive. Stability
was found to decrease in the sequence Ph Ͼ tBu Ͼ Cy Ͼ
It is commonly known that isocyanide molecules can be
regarded as ligands that have a lone pair of electrons at the
carbon atom like that in carbenes. Homobinuclear com-
plexes with isocyanide have recently been studied a great
[a] State Key Laboratory of Fine Chemicals, School of Chemical
Engineering, Dalian University of Technology,
Dalian 116012, People’s Republic of China
Fax: +86-411-8363-3080
1
Bn. The H NMR spectra of 2 in C6D6 show one broad
E-mail: qujp@dlut.edu.cn
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201000676.
signal at δ = 1.78, 1.79, 1.84, and 1.73 ppm, which is attrib-
uted to the Cp* protons for 2a, 2b, 2c, and 2d, respectively.
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P. Chen, Y. Peng, C. Jia, J. Qu
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The IR bands at 2099, 2058, and 1990 cm–1 (2a), 2089, PPh3 ligand. The structures of 3a, 3b, 3c, and 3d are unam-
2039, and 2001 cm–1 (2b), 2090, 2043, and 1998 cm–1 (2c), biguously characterized by single-crystal X-ray diffraction
and 2103, 2054, and 2004 cm–1 (2d) are indicative of the analysis, and their spectral features are fully consistent with
terminal end-on coordination mode of the CNR ligand.[8] their crystal structures. ORTEP drawings of the 3a and 3b
The EI-MS mass spectra give the parent peak at m/z = cations are shown in Figure 1 and Figure 2 (for 3c and 3d,
418.2104 for 2a, 458.1488 for 2b, 470.2421 for 2c, and see Figures S1 and S2 in the Supporting Information). Se-
486.1797 for 2d, and the successive loss of two isocyanide lected bond lengths and angles of 3a–3d are listed in
ligands before further fragmentation.
Table 1.
Scheme 1. Synthesis of complexes 2a, 2b, 2c, and 2d.
Synthesis and Characterization of [Cp*FeCNR(µ-CNR)(µ-
SEt)PdCl(PPh3)][PF6] (3a, R = tBu; 3b, R = Ph; 3c, R =
Cy; 3d, R = Bn)
Figure 1. ORTEP (ellipsoids at 30% probability) drawing of the
cation of 3a. All hydrogen atoms except for the hydrogen atoms at
We chose complex 2 as the starting material to investi-
gate its reactivity in the formation of heterometal com- C(29) are omitted for clarity.
plexes. As outlined in Scheme 2, treatment of [Cp*FeSEt-
(CNR)2] (2) with [PdCl2(PPh3)2] (1 equiv.) and AgPF6 in
THF at room temperature affords complexes [Cp*Fe-
CNR(µ-CNR)(µ-SEt)PdCl(PPh3)][PF6] (3a, R = tBu; 3b, R
= Ph; 3c, R = Cy; 3d, R = Bn) in 84, 92, 87, and 93% yields
(based on 2) as a dark violet-red microcrystalline solid,
respectively. Compounds 3a–3d displayed excellent solubi-
lity in acetonitrile, acetone, methonal, and tetrahydrofuran,
and are sparingly soluble in ether or hexane.
Figure 2. ORTEP (ellipsoids at 30% probability) drawing of the
cation of 3b. All hydrogen atoms except for the hydrogen atoms at
C(29) are omitted for clarity.
Scheme 2. Synthesis of complexes 3a, 3b, 3c, and 3d.
From the molecular structures of the cation of 3 we can
The 1H NMR spectra of 3a, 3b, 3c, and 3d in [D6]acetone see that two transition-metal fragments [Cp*Fe(CNR)] and
show a broad singlet at δ = 1.95, 2.12, 1.96, and 1.89 ppm, [PdCl(PPh3)] are bridged by an isocyanide ligand and a
which is attributed to the Cp* protons. The signals for CH2 thiolate ligand. To the best of our knowledge, complexes 3
protons of µ-SEt in 3a and 3c exhibit a quartet at δ = 1.53 are the first examples of a bridging isocyanide ligand be-
and 0.88 ppm, respectively, whereas two multiplets appear tween iron and palladium atoms. Ignoring the metal–metal
at δ = 1.82 and 1.61 ppm in 3b and at δ = 1.52 and 1.36 ppm bond, the geometry at the iron center is that of a three-
in 3d. Except for the signal of the PF6 anion, the 31P{1H} legged piano stool; it contains one terminal and one bridg-
NMR spectra of 3a, 3b, 3c, and 3d exhibit one signal at δ ing isocyanide group, as commonly observed in homonu-
= 30.2, 31.0, 29.7, and 29.4 ppm, respectively, due to the clear thiolate-bridged diiron complexes.[8] The Fe(1)–Pd(1)
5240
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Eur. J. Inorg. Chem. 2010, 5239–5246

Heteronuclear Thiolate Iron Complexes with Isocyanide Ligands
Table 1. Selected bond lengths [Å] and bond angles [°] of complexes complexes with Ni metal. Using complex [NiCl2(PPh3)2] as
3a–3d.
the substrate, we were able to achieve another new Fe–Ni
heterobinuclear complex. Complex 2a reacts readily with
[NiCl2(PPh3)2] (1 equiv.) and AgPF6 in THF at room tem-
perature to give complex [Cp*Fe(CNtBu)2(µ-SEt)NiCl-
(PPh3)][PF6] (4) in 75% yield (based on 2a) as a black-
brown microcrystalline solid (Scheme 3). When the above
reaction is performed respectively with complexes 2b, 2c, or
2d instead of 2a, we can get similar structural products with
different isocyanide ligands.
3a
C(31)–N(1)
C(32)–N(2)
Fe(1)–S(1)–Pd(1)
Fe(1)–C(31)–Pd(1)
S(1)–Fe(1)–C(31)
S(1)–Fe(1)–C(32)
S(1)–Pd(1)–C(31)
Fe(1)–Pd(1)
Fe(1)–S(1)
Fe(1)–C(31)
Fe(1)–C(32)
Pd(1)–S(1)
Pd(1)–P(1)
Pd(1)–C(31)
2.7409(7)
2.2099(12)
1.859(6)
1.153(6)
1.139(5)
76.49(4)
74.86(16)
102.75(13)
93.58(13)
83.38(12)
1.858(4)
2.2179(12)
2.2753(11)
2.558(4)
3b
Fe(1)–Pd(1)
Fe(1)–S(1)
Fe(1)–C(31)
Fe(1)–C(32)
Pd(1)–S(1)
Pd(1)–P(1)
Pd(1)–C(31)
2.7180(9)
2.2115(13)
1.861(5)
C(31)–N(1)
C(32)–N(2)
Fe(1)–S(1)–Pd(1)
Fe(1)–C(31)–Pd(1)
S(1)–Fe(1)–C(31)
S(1)–Fe(1)–C(32)
S(1)–Pd(1)–C(31)
1.166(5)
1.169(6)
75.34(4)
77.72(15)
105.21(13)
95.03(14)
88.29(11)
1.818(5)
2.2361(11)
2.2749(11)
2.416(4)
3c
Scheme 3. Synthesis of complex 4.
Fe(1)–Pd(1)
Fe(1)–S(1)
Fe(1)–C(31)
Fe(1)–C(32)
Pd(1)–S(1)
Pd(1)–P(1)
Pd(1)–C(31)
2.7139(11)
2.1999(10)
1.857(4)
C(31)–N(1)
C(32)–N(2)
Fe(1)–S(1)–Pd(1)
Fe(1)–C(31)–Pd(1)
S(1)–Fe(1)–C(31)
S(1)–Fe(1)–C(32)
S(1)–Pd(1)–C(31)
1.146(4)
1.150(4)
75.58(4)
74.28(12)
104.02(11)
93.77(11)
84.05(8)
The 1H NMR spectrum of 4 in CD3CN displays one
broad signal at δ = 2.59 ppm on account of the Cp* pro-
tons. Two broad signals at δ = 1.53 and 1.48 ppm are attrib-
uted to the two CNtBu ligand protons. Except for the signal
of the PF6 anion, the 31P{1H} NMR spectrum of 4 shows
one signal at δ = –5.9 ppm due to the PPh3 ligand. The
phosphane signal of PPh3 is shifted by about 36 ppm to a
higher field than that of 3a. In addition, the IR bands at
2157 and 2132 cm–1 offer clear evidence of the terminal
end-on coordination mode of the CNtBu ligand. The struc-
tural features of 4 were confirmed by single-crystal X-ray
diffraction analysis; the ORTEP drawing of the cation of 4
is shown in Figure 3. Selected bond lengths and angles of 4
are listed in Table 2.
1.848(4)
2.2287(9)
2.2736(11)
2.545(3)
3d
Fe(1)–Pd(1)
Fe(1)–S(1)
Fe(1)–C(31)
Fe(1)–C(32)
Pd(1)–S(1)
Pd(1)–P(1)
Pd(1)–C(31)
2.7368(10)
2.2169(13)
1.870(4)
C(31)–N(1)
C(32)–N(2)
Fe(1)–S(1)–Pd(1)
Fe(1)–C(31)–Pd(1)
S(1)–Fe(1)–C(31)
S(1)–Fe(1)–C(32)
S(1)–Pd(1)–C(31)
1.155(5)
1.151(5)
75.92(4)
78.26(15)
102.13(12)
93.50(12)
86.48(10)
1.852(4)
2.2323(11)
2.2650(10)
2.415(4)
bond length [2.7139(7)–2.7409(11) Å] of 3a–3d falls in the
2.5–2.8 Å range of those reported for heterobinuclear com-
plexes that contain Fe–Pd bonds.[11] Completely different
from the heterobinuclear Fe–Pt complexes [(CO)3Fe(µ-
CNR)(µ-dppm)Pt(PPh3)] with a bridging isocyanide ligand
that has a nearly equal distance to Fe and Pt atoms,[9] the
bridging isocyanide ligand in 3a–3d is clearly leaning to the
iron center, and the Fe(1)–C(31) [1.859(6)–1.870(4) Å] bond
lengths of 3a–3d are moderately shorter by 0.55–0.70 Å
than those of Pd(1)–C(31) [2.415(4)–2.558(4) Å]. In com-
plexes 3b–3d, the distance between Fe(1) and C(31) of the
bridging isocyanide ligand is apparently longer than that
between Fe(1) and C(32) of the terminal isocyanide ligand,
whereas the corresponding Fe(1)–C(31) and Fe(1)–C(32)
bond lengths in 3a are nearly equal. The Fe(1)Pd(1)C(31)-
S(1) rings of 3a–3d are substantially puckered with a dihe-
dral angle of 133.6, 144.5, 134.5, and 139.3°, respectively.
The Pd(1)–P(1) bond lengths [2.2650(10)–2.2753(11) Å] are
shorter than those found in the precursor trans-
[PdCl2(PPh3)2] [2.337(1) Å].[12]
Figure 3. ORTEP (ellipsoids at 30% probability) drawing of the
cation of 4. All hydrogen atoms are omitted for clarity.
Synthesis and Characterization of [Cp*Fe(CNtBu)2(µ-SEt)-
NiCl(PPh3)][PF6] (4)
Compared to the molecular structures of 3a–3d, with one
Encouraged by the successful syntheses of complexes 3, thiolate ligand and one isocyanide ligand bridging the two
we applied the synthetic method to other heteronuclear metal centers Fe and Pd, the structure of the cation of 4
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P. Chen, Y. Peng, C. Jia, J. Qu
FULL PAPER
Table 2. Selected bond lengths [Å] and bond angles [°] of 4.
Fe(1)–Ni(1)
Fe(1)–C(11)
Ni(1)–S(1)
Ni(1)–Cl(1)
C(16)–N(2)
S(1)–Fe(1)–C(11) 93.29(18)
S(1)–Ni(1)–P(1) 100.97(6)
2.6734(13)
1.851(6)
2.0952(17)
2.1926(18)
1.157(7)
Fe(1)–S(1)
Fe(1)–C(16)
Ni(1)–P(1)
C(11)–N(1)
Fe(1)–S(1)–Ni(1) 76.97(6)
S(1)–Fe(1)–C(16) 102.23(19)
P(1)–Ni(1)–Cl(1) 95.44(6)
2.1989(17)
1.851(6)
2.1910(17)
1.150(6)
shows only one bridging thiolate ligand between the Fe and
Ni atoms, and the other two isocyanide ligands are both
terminally coordinated to the Fe center. The Ni atom is
three-coordinate instead of four-coordinate as found in the
precursor. The rigid pyramidalization of the sulfur atom re-
sults in the two nonequivalent CNtBu ligands, which was
Scheme 4. Synthesis of complexes 5, 6, and 7. Reaction reagents
and conditions: THF, room temp., 12 h; 5: (Ph3P)AuCl (0.5 equiv.)
and AgPF6 (0.5 equiv.), 52%; 6 (method A): AgOTf (0.5 equiv.),
81%; (method B): (Ph3P)AgOTf (0.5 equiv.), 41%; 7 (method A):
(Ph3P)CuCl (0.5 equiv.) and AgPF6 (0.5 equiv.), 74%; (method B):
[CuPF6(MeCN)4] (0.5 equiv.), 86%.
1
also confirmed by H NMR spectroscopy. The Fe(1)–Ni(1)
bond length [2.6734(13) Å] is within the range (2.5–2.7 Å)
of those for heterobinuclear complexes that contain Fe–Ni
bonds.[13] The Ni(1)–P(1) bond length [2.1910(17) Å] is
shorter than that in mononuclear complex trans-
[NiCl2(PPh3)2] [2.2439(5) Å].[14]
compounds are retained in the products. The molecular
structures of 5, 6, and 7 are analogous except for the central
metal. For instance, the structure of 5 possesses a center of
inversion at the central metal center, which is coordinated
to two S donor atoms with a linear arrangement. The Cp*
rings are oriented on opposite sides of the S–Au–S line. In
the structures of 5, 6, and 7, there is no Fe–M metal–metal
bond (M = Au, Ag, or Cu). Thus, the flexible Fe(1)–S(1)
bond and C2 symmetry of the molecule result in the same
chemical environment of the four CNtBu ligands, which is
Synthesis and Characterization of [{Cp*Fe(CNtBu)2(µ-
SEt)}2M][PF6] (5, M = Au; 6, M = Ag; 7, M = Cu)
The successful synthesis of complexes 3 and 4 prompted
us to expand our synthetic approach to more challenging
systems that contain group 11 metals (Au, Ag, and Cu) as
the heterometals. To our surprise, we obtained three new
heterotrinuclear iron complexes that contained Au, Ag, and
Cu atoms. For example, treatment of 2a with (Ph3P)AuPF6
(0.5 equiv.) in THF at room temperature produced complex
[{Cp*Fe(CNtBu)2(µ-SEt)}2Au][PF6] (5) in moderate yield
as dark brown-red crystals (Scheme 4). The reaction did not
proceed at low temperature (from –78 to 0 °C). When 2a
was treated with (Ph3P)AuPF6 in a higher ratio of 6:1, we
still obtained 5 together with the unreacted 2a. In the same
way, by using AgOTf or (Ph3P)AgOTf and [CuPF6-
(MeCN)4] or (Ph3P)CuPF6 as the substrate, we were able to
get complexes [{Cp*Fe(CNtBu)2(µ-SEt)}2Ag][OTf] (6) and
[{Cp*Fe(CNtBu)2(µ-SEt)}2Cu][PF6] (7) in high yield. In
addition, analogous products could be achieved with dif-
ferent isocyanide ligands when the starting material 2a was
replaced by 2b, 2c, or 2d.
1
consistent with their H NMR spectra that show only one
signal for the four equivalent CNtBu ligands. The Fe(1)–
S(1) bond length [2.2883(19)–2.3016(11) Å] of 5, 6, and 7
is slightly longer than that of diiron complexes 1 (average:
Figure 4. ORTEP (ellipsoids at 30% probability) drawing of the
cation of 5. All hydrgen atoms are omitted for clarity.
The 1H NMR spectra of 5, 6, and 7 in CD3CN individu-
ally show a broad singlet at δ = 1.64, 1.60, and 1.61 ppm
attributed to two equivalent Cp* protons and one broad
signal at δ = 1.51, 1.49, and 1.48 ppm on account of four
equivalent CNtBu ligand protons. The IR spectrum of 5, 6,
and 7 (KBr) displays a strong band at 2050–2125 cm–1 on
account of NϵC stretching of the terminal CNtBu ligands.
Compared with that of 2a, the ν
bands of 5, 6, and 7
˜
NϵC
shift to higher wavenumbers.
The molecular structures of complexes 5, 6, and 7 have
been determined by single-crystal diffraction analyses and
are shown in Figures 4, 5, and 6. Significant bond param-
eters of 5, 6, and 7 are collectively given in Table 3. The
Figure 5. ORTEP (ellipsoids at 30% probability) drawing of the
oxidation states of all the metal atoms in the precursor cation of 6. All hydrogen atoms are omitted for clarity.
5242 Eur. J. Inorg. Chem. 2010, 5239–5246
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Heteronuclear Thiolate Iron Complexes with Isocyanide Ligands
and AgPF6 (or AgOTf) were available commercially and used with-
out further purification. The reagents CNtBu, CNPh, CNCy, and
CNBn were purchased from Aldrich. The starting material
[Cp*Fe(µ-SEt)3FeCp*] (1),[8] (Ph3P)CuCl,[15] (Ph3P)AgOTf,[16] and
(Ph3P)AuCl[17] were prepared according to the literature methods.
2.2638 Å), [Cp*FeSEt(µ-SEt)2FeCNtBuCp*] (average:
2.2615 Å), and [Cl2Fe(µ-SEt)2FeCNtBuCp*] (average:
2.2567 Å).[8]
The 1H and 31P NMR spectra were recorded with a Bruker 400
Ultra ShieldTM spectrometer. Chemical shifts are reported in ppm
1
externally referenced to SiMe4 for H and 85% H3PO4 for 31P nu-
clei. IR spectra were recorded with a JASCO FTIR 430 spectro-
photometer. HRMS (EI) spectra determinations were made with a
GCT-MS instrument (Micromass, England). ESI-MS spectra de-
terminations were made with a Micromass Q-Tof (Micromass,
Wythenshawe, UK) mass spectrometer. Elemental analyses were
performed with a Vario EL analyzer.
[Cp*FeSEt(CNtBu)2] (2a): CNtBu (145 mg, 1.747 mmol) was added
to a solution of 1 (190 mg, 0.336 mmol) in THF (10 mL). After
being stirred at room temperature for 12 h, the resulting black-
brown solution was evaporated to dryness in vacuo. The crude
product was purified by column chromatography on alumina using
Et2O/hexane (1:2) as eluent to give 2a as a dark red solid (175 mg,
Figure 6. ORTEP (ellipsoids at 30% probability) drawing of the
cation of 7. All hydrogen atoms are omitted for clarity.
Table 3. Selected bond lengths [Å] and bond angles [°] of 5, 6, and
7.
1
0.419 mmol, 63%). H NMR (400 MHz, C6D6): δ = 2.46 (q, J =
7.2 Hz, 2 H, CH2), 1.78 (br. s, 15 H, Cp*-CH3), 1.67 (t, J = 7.2 Hz,
5
6
7
Fe(1)–S(1)
Fe(1)–C(11)
Fe(1)–C(16)
M(1)–S(1)
C(11)–N(1)
C(16)–N(2)
2.2950(17)
1.834(7)
1.829(7)
2.3086(17)
1.148(8)
1.147(8)
180.00(2)
108.70(6)
102.3(2)
89.2(3)
2.3016(11)
1.828(3)
1.824(3)
2.3842(12)
1.161(4)
1.154(4)
180.00(4)
106.25(4)
101.74(12)
89.79(13)
91.45(10)
95.13(10)
2.2883(19)
1.786(6)
1.812(6)
2.260(2)
1.158(7)
1.180(7)
180.00(8)
106.48(7)
102.8(2)
89.8(2)
3 H, CH ), 1.19 (s, 18 H, tBu) ppm. IR (KBr ): ν = 2971 (w), 2910
˜
3
(w), 2860 (vw), 2099 (vs), 2058 (vs), 1990 (vs), 1454 (m), 1366 (m),
1229 (m), 1211 (w), 1026 (w), 882 (w), 744 (m), 558 (m), 527 (m),
464 (w) cm–1. HRMS (EI): calcd. for [M]+ 418.2105; found
418.2104. C22H38FeN2S (418.46): calcd. C 63.14, H 9.15, N 6.69;
found C 63.15, H 9.17, N 6.70.
S(1)–M(1)–S(1)#1
Fe(1)–S(1)–M(1)
C(21)–S(1)–M(1)
C(11)–Fe(1)–C(16)
S(1)–Fe(1)–C(11)
S(1)–Fe(1)–C(16)
[Cp*FeSEt(CNPh)2] (2b): The reaction was carried out analogously
to the procedure described for 2a by treatment of 1 (606 mg,
1.073 mmol) with CNPh (560 mg, 5.437 mmol). After the purifica-
tion by column chromatography on alumina, 2b (791 mg,
1.727 mmol, 81%) was obtained as a dark red solid. 1H NMR
(400 MHz, C6D6): δ = 7.18–6.74 (m, 10 H, Ph), 2.66 (q, J = 8.0 Hz,
2 H, CH2), 1.79 (br. s, 15 H, Cp*-CH3), 1.65 (t, J = 8.0 Hz, 3 H,
91.7(2)
95.12(18)
91.90(19)
95.04(17)
CH ) ppm. IR (KBr ): ν = 2957 (w), 2904 (w), 2089 (vs), 2039 (vs),
˜
3
Conclusion
2001 (vs), 1591 (m), 1488 (m), 1454 (w), 1375 (w), 1262 (vw), 1070
(w), 1024 (w), 803 (w), 750 (m), 684 (m), 569 (m), 534 (w), 487
(w) cm–1. HRMS (EI): calcd. for [M]+ 458.1479; found 458.1488.
C26H30FeN2S (458.44): calcd. C 68.12, H 6.60, N 6.11; found C
68.14, H 6.63, N 6.12.
In summary, we have successfully synthesized four
heterobinuclear complexes that contain the Pd atom,
[Cp*FeCNR(µ-CNR)(µ-SEt)PdCl(PPh3)][PF6] (3a, R =
tBu; 3b, R = Ph; 3c, R = Cy; 3d, R = Bn), one heterobi-
nuclear Fe–Ni complex, [Cp*Fe(CNtBu)2(µ-SEt)NiCl-
(PPh3)][PF6] (4), and three heterotrinuclear complexes that
contain Au, Ag, and Cu atoms, [{Cp*Fe(CNtBu)2(µ-
SEt)}2M][PF6] (5, M = Au; 6, M = Ag; 7, M = Cu). It is
noteworthy that this is the first time that heterobinuclear
Fe–Pd complexes with bridging isocyanide and thiolate-
linked heterotrinuclear Fe–SEt–M–SEt–Fe (M = Au and
Ag) complexes have been reported. Such complexes with
Cp* ligands and heterometals may show some remarkable
properties in catalytic transformation and material science.
Further investigations toward the synthesis of complexes
with other heterometals are now in progress.
[Cp*FeSEt(CNCy)2] (2c): The reaction was carried out analogously
to the procedures described for 2a by treatment of 1 (160 mg,
0.283 mmol) with CNCy (160 mg, 1.468 mmol). After the purifica-
tion by column chromatography on alumina, 2c (225 mg,
0.479 mmol, 85%) was obtained as a dark red solid. 1H NMR
(400 MHz, C6D6): δ = 2.51 (q, J = 7.2 Hz, 2 H, CH2), 1.84 (br. s,
15 H, Cp*-CH3), 1.71 (t, J = 7.2 Hz, 3 H, CH3), 1.69–0.95 (m, 22
H, cyclo-C H ) ppm. IR (KBr ): ν = 2935 (w), 2855 (w), 2090 (vs),
˜
6
11
2043 (vs), 1998 (vs), 1450 (m), 1362 (m), 1320 (m), 1261 (m), 1095
(m), 1025 (m), 891 (w), 863 (w), 801 (m), 659 (m), 582 (w), 531
(w), 494 (vw) cm–1. HRMS (EI): calcd. for [M]+ 470.2418; found
470.2424. C26H42FeN2S (470.54): calcd. C 66.37, H 9.00, N 5.95;
found C 66.40, H 9.03, N 5.96.
[Cp*FeSEt(CNBn)2] (2d): The reaction was carried out analogously
to the procedures described for 2a by treatment of 1 (328 mg,
0.581 mmol) with CNBn (350 mg, 2.986 mmol). After the purifica-
tion by column chromatography on alumina, 2d (380 mg,
0.782 mmol, 67%) was obtained as a dark red solid. 1H NMR
(400 MHz, C6D6): δ = 7.25–7.00 (m, 10 H, Ph), 4.28 (dd, J =
16.8 Hz, 4 H, CH2), 2.50 (q, J = 7.2 Hz, 2 H, CH2), 1.73 (br. s, 15
Experimental Section
General: All manipulations were routinely carried out under an ar-
gon atmosphere, using standard Schlenk-line techniques. All sol-
vents were dried and distilled from an appropriate drying agent
under argon. [PdCl2(PPh3)2], [NiCl2(PPh3)2], [CuPF6(MeCN)4],
H, Cp*-CH ), 1.68 (t, J = 7.2 Hz, 3 H, CH ) ppm. IR (KBr ): ν =
˜
3
3
Eur. J. Inorg. Chem. 2010, 5239–5246
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
5243

P. Chen, Y. Peng, C. Jia, J. Qu
FULL PAPER
3064 (vw), 3030 (vw), 2951 (w), 2907 (m), 2854 (vw), 2103 (vs), (333 mg, 0.322 mmol, 93%) as a dark violet-red crystals. 1H NMR
2054 (vs), 2004 (vs), 1605 (vw), 1496 (m), 1454 (w), 1375 (w), 1348 (400 MHz, [D6]acetone): δ = 7.76–7.41 (m, 25 H, Ph), 5.52 (dd, J
(m), 1302 (vw), 1244 (w), 1029 (m), 801 (w), 733 (m), 697 (m), 598 = 16.0 Hz, 2 H, CH2), 5.27 (dd, J = 16.0 Hz, 2 H, CH2), 1.89 (br.
(m), 508 (w) cm–1. HRMS (EI): calcd. for [M]+ 486.1792; found
486.1797. C28H34FeN2S (486.49): calcd. C 69.13, H 7.04, N 5.76;
found C 69.14, H 7.06, N 5.77.
s, 15 H, Cp*-CH3), 1.52 (m, 1 H, CH2), 1.36 (m, 1 H, CH2), 0.55
(t, J = 8.0 Hz, 3 H, CH3) ppm. 31P{1H} NMR (162 MHz, [D6]-
acetone): δ = 29.4 (s, PPh ), –144.3 (sept, PF ) ppm. IR (KBr ): ν
˜
3
6
= 3049 (w), 2920 (w), 2169 (vs), 2086 (vs), 1496 (vw), 1481 (w),
1453 (w), 1435 (m), 1381 (w), 1347 (w), 1097 (m), 1026 (m), 840
(vs), 748 (w), 739 (w), 695 (m), 558 (m), 532 (m), 508 (m), 477 (vw),
450 (w) cm–1. HRMS (ESI): calcd. for [M – PF6]+ 889.1427; found
889.1432. C46H49ClF6FeN2P2PdS (1035.62): calcd. C 53.35, H 4.77,
N 2.70; found C 53.38, H 4.80, N 2.76.
[Cp*FeCNtBu(µ-CNtBu)(µ-SEt)PdCl(PPh3)][PF6] (3a): A solution
of AgPF6 (92 mg, 0.364 mmol) in THF (2 mL) was added to a sus-
pension of [PdCl2(PPh3)2] (250 mg, 0.356 mmol) in THF (10 mL)
and the resulting solution was stirred for about 3 h. A solution of
2a (152 mg, 0.364 mg) in THF (3 mL) was added to the reaction
mixture, and the resulting violet-red suspension was stirred in the
darkness at room temperature for 12 h. After filtration and removal
of the solvent in vacuo, the residue was washed with Et2O
(2ϫ10 mL) and then extracted with acetone. Addition of Et2O to
the concentrated acetone solution afforded 3a (296 mg,
[Cp*Fe(CNtBu)2(µ-SEt)NiCl(PPh3)][PF6] (4): A solution of AgPF6
(101 mg, 0.399 mmol) in THF (4 mL) was added to a suspension
of [NiCl2(PPh3)2] (250 mg, 0.382 mmol) in THF (15 mL) and the
resulting solution was stirred for about 3 h. A solution of 2a
(160 mg, 0.383 mmol) in THF (5 mL) was added to the reaction
mixture, and the resulting brown-yellow suspension was stirred in
the darkness at room temperature for 12 h. After filtration and re-
moval of the solvent in vacuo, the residue was washed with Et2O
(2ϫ10 mL) and then extracted with acetone. Addition of Et2O to
the concentrated acetone solution afforded 4 (264 mg, 0.288 mmol,
75%) as a dark brown-yellow crystals. 1H NMR (400 MHz,
0.306 mmol, 84%) as
a
dark violet-red crystals. 1H NMR
(400 MHz, [D6]acetone): δ = 7.85–7.52 (m, 15 H, Ph), 1.95 (br. s,
15 H, Cp*-CH3), 1.70 (s, 9 H, tBu), 1.60 (s, 9 H, tBu), 1.53 (q, J
= 8.0 Hz, 2 H, CH2), 0.81 (t, J = 8.0 Hz, 3 H, CH3) ppm. 31P{1H}
NMR (162 MHz, [D6]acetone): δ = 30.2 (s, PPh3), –144.3 (sept,
PF ) ppm. IR (KBr ): ν = 3057 (vw), 2980 (w), 2158 (s), 2124 (m),
˜
6
1481 (w), 1437 (m), 1372 (vw), 1191 (w), 1097 (m), 842 (vs), 750
(w), 694 (m), 558 (m), 526 (m), 509 (vw), 472 (vw) cm–1. HRMS CD3CN): δ = 7.80–7.29 (m, 15 H, Ph), 2.59 (br. s, 15 H, Cp*-CH3),
(ESI): calcd. for [M
–
PF6]+ 821.1740; found 821.1747.
1.53 (br., 9 H, tBu), 1.48 (br., 9 H, tBu), 1.27 (br., 2 H, CH2), 0.79
C44H61ClF6FeN2OP2PdS (1039.69): calcd. C 50.83, H 5.91, N 2.69;
found C 50.86, H 5.95, N 2.71.
(br., 3 H, CH3) ppm. 31P{1H} NMR (162 MHz, CD3CN): δ = –5.9
(s, PPh ), –144.7 (sept, PF ) ppm. IR (KBr ): ν = 3056 (vw), 2979
˜
3
6
(w), 2157 (vs), 2132 (vs), 1484 (m), 1458 (w), 1438 (m), 1372 (m),
1262 (w), 1190 (m), 1095 (m), 1023 (w), 840 (vs), 754 (m), 697 (m),
558 (s), 526 (s), 510 (m), 494 (w), 469 (w) cm–1. HRMS (ESI): calcd.
for [M – PF6]+ 773.2058; found 773.2065. C40H55ClF6FeN2NiOP2S
(937.87): calcd. C 51.23, H 5.91, N 2.99; found C 51.24, H 5.93, N
3.01.
[Cp*FeCNPh(µ-CNPh)(µ-SEt)PdCl(PPh3)][PF6] (3b): The reaction
was carried out analogously to the procedures described for 3a by
treatment of 2b (152 mg, 0.332 mmol) with [PdCl2(PPh3)2] (233 mg,
0.332 mmol) and AgPF6 (87 mg, 0.344 mmol), and gave 3b
(306 mg, 0.304 mmol, 92%) as a dark violet-red crystals. 1H NMR
(400 MHz, [D6]acetone): δ = 7.85–7.47 (m, 25 H, Ph), 2.12 (br. s,
15 H, Cp*-CH3), 1.82 (m, 1 H, CH2), 1.61 (m, 1 H, CH2), 0.87 (t, [{Cp*Fe(CNtBu)2(µ-SEt)}2Au][PF6] (5):
A solution of AgPF6
J = 8.0 Hz, 3 H, CH3) ppm. 31P{1H} NMR (162 MHz, [D6]ace- (110 mg, 0.435 mmol) in THF (4 mL) was added to a solution of
tone): δ = 31.0 (s, PPh ), –144.3 (sept, PF ) ppm. IR (KBr ): ν =
(Ph3P)AuCl (215 mg, 0.434 mmol) in THF (8 mL) and stirred at
˜
3
6
3061 (vw), 2924 (m), 2854 (w), 2125 (vs), 2112 (vs), 2060 (vs), 1631
0 °C for about 1 h. A solution of 2a (365 mg, 0.873 mmol) in THF
(w), 1589 (m), 1482 (m), 1454 (w), 1435 (m), 1380 (m), 1161 (vw), (4 mL) was added to the reaction mixture, and the resulting dark
1096 (m), 1024 (w), 843 (vs), 759 (m), 693 (m), 558 (m), 529 (w), brown-red suspension was stirred in the darkness at room tempera-
519 (vw), 495 (vw) cm–1. HRMS (ESI): calcd. for [M – PF6]+ ture for 12 h. After removal of the solvent in vacuo, the residue
861.1114; found 861.1123. C44H45ClF6FeN2P2PdS (1007.56): calcd.
C 52.45, H 4.50, N 2.78; found C 52.49, H 4.55, N 2.79.
was washed with Et2O (3ϫ8 mL) and then extracted with THF.
Addition of Et2O to the concentrated THF solution afforded 5
(263 mg, 0.223 mmol, 52%) as a dark brown-red crystals. 1H NMR
(400 MHz, CD3CN): δ = 2.34 (q, J = 8.0 Hz, 4 H, CH2), 1.64 (br.
s, 30 H, Cp*-CH3), 1.51 (s, 36 H, tBu), 1.28 (t, J = 8.0 Hz, 6 H,
CH3) ppm. 31P{1H} NMR (162 MHz, CD3CN): δ = –144.7 (sept,
[Cp*FeCNCy(µ-CNCy)(µ-SEt)PdCl(PPh3)][PF6] (3c): The reaction
was carried out analogously to the procedures described for 3a by
treatment of 2c (259 mg, 0.551 mmol) with [PdCl2(PPh3)2] (388 mg,
0.553 mmol) and AgPF6 (140 mg, 0.553 mmol), and gave 3c
(488 mg, 0.479 mmol, 87%) as a dark violet-red crystals. 1H NMR
(400 MHz, [D6]acetone): δ = 7.85–7.54 (m, 15 H, Ph), 4.55 (t, J =
8.0 Hz, 1 H, CH), 4.28 (t, J = 8.0 Hz, 1 H, CH), 1.96 (br. s, 15 H,
Cp*-CH3), 1.79–1.29 (m, 20 H, cyclo-C6H11), 0.88 (q, J = 8.0 Hz,
2 H, CH2), 0.79 (t, J = 8.0 Hz, 3 H, CH3) ppm. 31P{1H} NMR
(162 MHz, [D6]acetone): δ = 29.7 (s, PPh3), –144.3 (sept, PF6) ppm.
PF ) ppm. IR (KBr ): ν = 2978 (m), 2922 (w), 2123 (vs), 2089 (vs),
˜
6
2050 (vs), 1459 (m), 1398 (w), 1371 (m), 1235 (w), 1210 (m), 1028
(vw), 840 (vs), 557 (m), 536 (w), 486 (w) cm–1. HRMS (ESI): calcd.
for [M – PF6]+ 1033.3876; found 1033.3884. C44H76AuF6Fe2N4PS2
(1178.85): calcd. C 44.83, H 6.50, N 4.75; found C 44.86, H 6.57,
N 4.79.
IR (KBr ): ν = 2934 (w), 2859 (vw), 2179 (vs), 2140 (vw), 2107
[{Cp*Fe(CNtBu)2(µ-SEt)}2Ag][OTf] (6). Method A: A solution of
AgOTf (84 mg, 0.327 mmol) in THF (5 mL) was added to a solu-
tion of 2a (273 mg, 0.653 mmol) in THF (5 mL). The resulting
brown-red solution was stirred in the darkness at room temperature
for 12 h. After removal of the solvent in vacuo, the residue was
washed with Et2O (2ϫ5 mL) and extracted with THF. Addition of
Et2O to the concentrated THF solution afforded 6 (287 mg,
0.263 mmol, 81%) as a dark brown-red crystals.
˜
(vw), 1482 (w), 1436 (m), 1367 (w), 1096 (m), 1026 (vw), 840 (vs),
746 (w), 696 (m), 557 (m), 530 (m), 510 (m), 448 (vw) cm–1. HRMS
(ESI): calcd. for [M
–
PF6]+ 873.2053; found 873.2057.
C44H57ClF6FeN2P2PdS (1019.66): calcd. C 51.83, H 5.63, N 2.75;
found C 51.88, H 5.65, N 2.79.
[Cp*FeCNBn(µ-CNBn)(µ-SEt)PdCl(PPh3)][PF6] (3d): The reaction
was carried out analogously to the procedures described for 3a by
treatment of 2d (168 mg, 0.346 mmol) with [PdCl2(PPh3)2] (243 mg, Method B: A solution of (Ph3P)AgOTf (192 mg, 0.370 mmol) in
0.346 mmol) and AgPF6 (88 mg, 0.348 mmol), and gave 3d THF (5 mL) was added to a solution of 2a (310 mg, 0.742 mmol)
5244
www.eurjic.org
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2010, 5239–5246

Heteronuclear Thiolate Iron Complexes with Isocyanide Ligands
in THF (5 mL). The resulting violet-red solution was stirred in the
darkness at room temperature for 12 h. After filtration and removal
of the solvent in vacuo, the residue was washed with Et2O
(2ϫ5 mL) and extracted with THF. Addition of Et2O to the con-
centrated THF solution afforded 6 (166 mg, 0.152 mmol, 41%) as
a dark brown-red crystals. 1H NMR (400 MHz, CD3CN): δ = 2.11
(br., 4 H, CH2), 1.60 (br., 30 H, Cp*-CH3), 1.49 (s, 36 H, tBu),
(vs), 2051 (vs), 1460 (m), 1371 (m), 1235 (w), 1210 (m), 1071 (vw),
1028 (w), 840 (vs), 770 (w), 743 (w), 557 (m), 536 (w), 482 (m)
cm–1. HRMS (ESI): calcd. for [M – PF6]+ 899.3506; found
899.3509. C44H76CuF6Fe2N4PS2 (1045.43): calcd. C 50.55, H 7.33,
N 5.36; found C 50.56, H 7.37, N 5.39.
X-ray Data Collection and Structure Refinement: The data were ob-
tained with a Bruker SMART APEX CCD diffractometer with
graphite-monochromated Mo-Kα radiation (λ = 0.71073 Å). Em-
pirical absorption corrections were performed using the SADABS
program.[18] Structures were solved by direct methods and refined
by full-matrix least-squares based on all data using F2 using
SHELX97.[19] All of the non-hydrogen atoms were refined with an-
isotropic thermal displacement coefficients. Hydrogen atoms were
fitted geometrically at calculated distances and allowed to ride on
the parent non-hydrogen atoms with the isotropic displacement be-
ing fixed at 1.2 and 1.5 times the aromatic and methyl carbon
atoms that attached, respectively. The SEt ligand in 4, and one of
CNtBu ligands in 5, 6, and 7 were disordered and restrained during
refinement of the structure. Disordered atomic positions were split
into two parts and refined using one occupancy parameter per dis-
ordered group. Crystal data and collection details for the X-ray
structure determinations are summarized in Table 4.
1.25 (br., 6 H, CH ) ppm. IR (KBr ): ν = 2975 (m), 2914 (w), 2114
˜
3
(vs), 2052 (vs), 1456 (m), 1369 (m), 1272 (vs), 1207 (m), 1144 (m),
1031 (s), 741 (w), 638 (s), 535 (vw), 516 (w) cm–1. HRMS (ESI):
calcd. for [M – PF6]+ 943.3261; found 943.3265. C45H76AgF3F-
e2N4O3S3 (1093.86): calcd. C 49.41, H 7.00, N 5.12; found C 49.46,
H 7.06, N 5.17.
[{Cp*Fe(CNtBu)2(µ-SEt)}2Cu][PF6] (7). Method A: A solution of
AgPF6 (134 mg, 0.530 mmol) in THF (5 mL) was added to a solu-
tion of (Ph3P)CuCl (188 mg, 0.521 mmol) in THF (15 mL) and
stirred for about 2 h. A solution of 2a (438 mg, 1.048 mmol) in
THF (5 mL) was added to the reaction mixture, and the resulting
dark red suspension was stirred in the darkness at room tempera-
ture for 12 h. After removal of the solvent in vacuo, the residue
was washed with Et2O (2ϫ5 mL) and then extracted with THF.
Addition of Et2O to the concentrated THF solution afforded 7
(406 mg, 0.389 mmol, 74%) as a dark brown-red crystals.
Method B: A solution of [CuPF6(CH3CN)4] (115 mg, 0.308 mmol)
in THF (8 mL) was added to a solution of 2a (258 mg, 0.617 mmol)
in THF (2 mL). The resulting brown-red solution was stirred in the
darkness at room temperature for 12 h. After removal of the sol-
vent in vacuo, the residue was washed with Et2O (2ϫ5 mL) and
extracted with THF. Addition of Et2O to the concentrated THF
solution afforded 7 (275 mg, 0.263 mmol, 86%) as a dark brown-
red crystals. 1H NMR (400 MHz, CD3CN): δ = 2.07 (q, J = 7.2 Hz,
CCDC-773332 (for 3a), -773333 (for 3b), -773334 (for 3c), -773335
(for 3d), -773336 (for 4), -773337 (for 7), -773338 (for 6) and
-773339 (for 5) contain the supplementary crystallographic data for
this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
Supporting Information (see also the footnote on the first page of
4 H, CH2), 1.61 (br. s, 30 H, Cp*-CH3), 1.48 (s, 36 H, tBu), 1.23 (t, this article): ORTEP drawings of complexes 3c and 3d. The 1H
J = 7.2 Hz, 6 H, CH3) ppm. 31P{1H} NMR (162 MHz, CD3CN): δ NMR and IR spectra of complexes 2, 3, 4, 5, 6, and 7. The 31P{1H}
= –144.7 (sept, PF ) ppm. IR (KBr ): ν = 2978 (m), 2920 (w), 2119
NMR spectra of complexes 3 and 4.
˜
6
Table 4. Crystal data and structure refinements for 3a, 3b, 4, 5, 6, and 7.
3a·THF
3b
4·H2O
5
6
7
Empirical formula
C44H61ClF6-
FeN2OP2PdS
1039.65
C44H45ClF6-
FeN2P2PdS
1007.52
C40H55ClF6-
FeN2NiOP2S
937.87
C44H76AuF6-
Fe2N4PS2
1178.84
C45H76AgF3-
Fe2N4O3S3
1093.85
C44H76CuF6-
Fe2N4PS2
1045.42
Formula weight
T [K]
293(2)
293(2)
293(2)
293(2)
293(2)
293(2)
Crystal size [mm]
Crystal system
Space group
a [Å]
b [Å]
c [Å]
0.59ϫ0.36ϫ0.24
monoclinic
P21/c
11.6205(17)
19.828(3)
21.404(3)
94.457(9)
4916.6(12)
4
0.35ϫ0.14ϫ0.10 0.23ϫ0.21ϫ0.18 0.41ϫ0.26ϫ0.15 0.78ϫ0.64ϫ0.24 0.35ϫ0.26ϫ0.18
monoclinic
P21/c
monoclinic
P21/c
triclinic
P1
triclinic
P1
triclinic
P1
¯
¯
¯
9.223(3)
27.678(9)
18.199(6)
101.133(6)
4558(3)
4
11.600(5)
19.788(8)
21.125(9)
94.560(6)
4833(4)
4
9.289(4)
11.200(4)
14.281(5)
76.333(4)
1348.3(9)
1
9.347(4)
11.274(5)
14.401(6)
77.255(4)
1382.5(10)
1
9.216(6)
11.158(7)
14.292(9)
76.323(10)
1329.2(14)
1
β [°]
V [Å3]
Z
dc [gcm–3]
1.405
0.879
1.468
1.289
1.452
1.314
1.306
µ [mm–1]
0.944
0.907
3.404
1.029
1.097
F(000)
2144
2048
1952
600
572
550
θmax [°]
26.25
25.00
25.00
26.67
25.00
25.00
Reflections collected
Reflections unique
Rint
25017
8601
0.0450
1.051
R1 = 0.0526,
wR2 = 0.1166
R1 = 0.0825,
wR2 = 0.1262
0.889/–0.497
21999
8010
0.0508
1.062
R1 = 0.0448,
wR2 = 0.1077
R1 = 0.0683,
wR2 = 0.1175
0.606/–0.515
23881
8507
0.0589
0.992
R1 = 0.0684,
wR2 = 0.1876
R1 = 0.1210,
wR2 = 0.2127
0.692/–0.430
6724
4637
0.0256
1.027
R1 = 0.0474,
wR2 = 0.1200
R1 = 0.0572,
wR2 = 0.1250
1.491/–1.691
6730
4728
0.0187
1.059
R1 = 0.0357,
wR2 = 0.0982
R1 = 0.0428,
wR2 = 0.1025
0.513/–0.399
6503
4616
0.0163
1.057
R1 = 0.0619,
wR2 = 0.2003
R1 = 0.0806,
wR2 = 0.2173
1.608/–0.640
GOF(F2)
R indices [IϾ2σ(I)][a]
R indices (all data)[b]
Residuals [eÅ–3]
[a] R1 = Σ||Fo| – |Fc||/Σ|Fo|. [b] wR2 = {Σ[w(Fo – Fc ) ]/Σ[w(Fo2)2]}1/2
.
2
2 2
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Acknowledgments
This work was financially supported by the National Natural Sci-
ence Foundation of China (grant numbers 20972023, 20944003),
the Program for Changjiang Scholars and Innovative Research
Team in University (grant number IRT0711), and the Fundamental
Research Funds for the Central Universities.
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Received: June 22, 2010
Published Online: October 18, 2010
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Eur. J. Inorg. Chem. 2010, 5239–5246