Synthesis, molecular structure and reactivity of new π-conjugated diyne with ferrocenyl and phenyl units

Article abstract of DOI:10.1016/j.poly.2006.09.044

New π-conjugated butadiynyl ligand FcC(CH₃)₂Fc′-C{triple bond, long}C-C{triple bond, long}C-Ph (L₁) has been synthesized and its reaction with Co₂(CO)₈ has been studied. New clusters [FcC(CH₃

Full text of DOI:10.1016/j.poly.2006.09.044

Polyhedron 26 (2007) 981–988
www.elsevier.com/locate/poly
Synthesis, molecular structure and reactivity of new p-conjugated
diyne with ferrocenyl and phenyl units
a
a,
a
a
Ning Zhu , Quan-Ling Suo *, Yi-Bing Wang , Li-Min Han ,
a
b
Yue-Guang Bai , Lin-Hong Weng
a
Chemical Engineering College, Inner Mongolia University of Technology, Hohhot 010051, PR China
b
Department of Chemistry, Fudan University, Shanghai 200433, PR China
Received 7 August 2006; accepted 22 September 2006
Available online 28 September 2006
Abstract
New p-conjugated butadiynyl ligand FcC(CH3)2Fc0–C„C–C„C–Ph (L1) has been synthesized and its reaction with Co2(CO)8 has
been studied. New clusters [FcC(CH3)2Fc0–C„C–C„C–Ph][Co2(CO)6]n [(1): n = 1; (2): n = 2] and [Fc–C„C–C„C–Ph][Co2(CO)6]n
[(3): n = 1; (4): n = 2] were obtained by the reaction of ligands FcC(CH3)2Fc0–C„C–C„C–Ph (L1) and Fc–C„C–C„C–Ph (L2) with
Co2(CO)8 respectively and the composition and structure of the clusters and ligands have been characterized by elemental analysis,
1
FTIR, H and 13C NMR and MS. The crystal structures of compounds L1, L2, 2 and 4 have been determined by X-ray single crystal
analysis.
ꢀ 2006 Elsevier Ltd. All rights reserved.
Keywords: Ferrocenyl diyne ligand; Cobalt carbonyl complex; Molecular structure of ferrocene derivative; Reactivity of butadiynyl group
1. Introduction
the redox potentials of the ferrocenyl groups in the com-
plexes have received considerable attention [18–20], there-
fore, the molecular design and synthesis of ferrocene
derivatives with the unsaturated C4 diyne chain are signif-
icance. The butadiynyl compounds substituted by phenyl
group at one terminating end and ferrocenyl group at
another terminal are rare but the compounds are an
approach to construct such linear donor-p-conjugated
spacer-acceptor assembly while the terminating phenyl
group is coordinated with metal carbonyl compound [21].
Herein a new ligand L1 was designed and prepared by
the cross coupling reaction. The ligand L2 was obtained
by the different route from literature [21], furthermore,the
molecular and crystal structures of L2 have firstly been
reported. New complexes 1, 2, 3 and 4 were synthesized
by the reactions of L1 and L2 with Co2(CO)8 respectively.
We also describe the structural characterization of
compounds L1, L2, 1, 2, 3 and 4, in which molecular and
crystal structures of compounds L1, L2, 2 and 4 have been
discussed in detail.
The chemistry of ferrocene derivatives is still an active
research field and a number of articles on this subject have
appeared [1–5]. Researches into the syntheses and electro-
chemical properties of ferrocenylbutadiyne compounds
and their complexes continue to develop as a key area of
organometallic chemistry [6–11]. Linear compounds with
redox-active organometallic terminal linked by p-conju-
gated polyynes are of current interest as candidates for
molecular wire materials that allow electron transfer to
occur along the molecular backbones [12–15]. The ferroce-
nyl groups bridged by the C4 diyne chain have been
recognized as good model system for the electronic com-
munication between the two ferrocenyl units [16,17]. The
effects of the metal carbonyl cluster units of coordination
on the p-bonding of the unsaturated C4 diyne chain on
*
Corresponding author.
E-mail address: szj@imut.edu.cn (Q.-L. Suo).
0277-5387/$ - see front matter ꢀ 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2006.09.044

982
N. Zhu et al. / Polyhedron 26 (2007) 981–988
2. Experimental
2.1. General procedures
reduced pressure. The resulting mixture was washed
with saturated NH4Cl solution and extracted with
CH2Cl2.The organic phase was incorporated and then
dried using the dehydrated MgSO4 and filtrated. The fil-
trate was concentrated and the residue was subjected to
chromatographic separation on the neutral alumina col-
umn (2.0 · 30 cm). Elution with a mixture of hexane–
benzene (3:1, v/v) afforded a yellow band. The yellow
crystal of ligand L2 was obtained by recrystallizing from
hexane. Yield: 47% (73 mg, 0.24 mmol). m.p. 114–115 ꢁC.
Anal. Calc. for C20H14Fe: C, 77.45; H, 4.55. Found: C,
77.60; H, 4.70%. IR (KBr disk) 3083 [Cp, mC–H]; 2218,
2145 [C„C, mC„C]; 1593, 1490, 1441 [C6H5, mC@C];
1104, 1001 [Cp, cC–H]; 817 [Cp, dC–H]; 755, 688 [C6H5,
All reactions and manipulations were carried out using
standard Schlenk techniques under an atmosphere of pure
nitrogen. Solvents were purified, dried and distilled under a
nitrogen atmosphere prior to use. Reactions were moni-
tored by TLC. Chromatographic separations and purifica-
tion were performed on 200-300 mesh silica gel column.
The Co2(CO)8 was purchased from Aldrich. Published pro-
cedures or extensions thereof were used to synthesize initial
intermediates FcC(CH3)2Fc0–C„CH and FcC„CH
[22–24].
IR spectra were recorded on a Nicolet FT-IR spectrom-
eter, KBr disk. Elemental analyses were carried out on a
Elementar var III-type analyzer. 1H and 13C NMR spectra
in CDCl3 were recorded on Inova-500 MHz spectrometer.
The mass spectra were determined by using Polaris Q
MS, Autospec Ultima-TOF and JMS-T100LC instru-
ments. Melting points were determined by using XT-4
melting point apparatus.
c .
C–H] cmꢀ1 1H NMR (CDCl3, d): 7.3–7.5 (m, 5H,
C6H5), 4.3, 4.6 (2s, 9H, Cp). 13C NMR (CDCl3, d):
132.3, 128.8, 128.4, 122.2 (C6H5); 82.1, 78.9, 74.7, 72.3
(–C„C–C„C–); 70.3, 70.1, 69.6, 63.2 (Cp). MS (EI):
310 (M+).
2.4. Synthesis of complex [FcC(CH3)2Fc0–C„C–C„C–
Ph][Co2(CO)6] (1)
2.2. Synthesis of ligand FcC(CH3)2Fc0–C„C–C„C–Ph
(L1)
A benzene solution of Co2(CO)8 (45 mg, 0.13 mmol) and
ligand L1 (70 mg, 0.13 mmol) was stirred for 12 h at room
temperature. The solvent of the resulting mixture was
removed in vacuum. The residue was dissolved in a mini-
mal amount of benzene and subjected to chromatographic
separation on a silica gel column (2.0 · 40 cm). Elution
with hexane–benzene (5:1,v/v) afforded four bands, respec-
tively. The first band is red by-product [Ph–C„C–C„C–
Ph][Co2(CO)6]2 (14 mg); the second band is the brown-
green complex 2 (15 mg); the third and fourth bands
are coordinated isomers [FcC(CH3)2Fc0–C„C–C2–Ph]-
[Co2(CO)6] [brown-green oil, Yield: 28% (30 mg,
0.04 mmol); Anal. Calc. for C39H28O6Co2Fe2: C, 56.97;
H, 3.43. Found: C, 57.69; H, 3.74%. IR (KBr disk) m
(CO) 2089s, 2056vs, 2025vs cmꢀ1; mC„C 2172w cmꢀ1].
and [FcC(CH3)2Fc0–C2–C„C–Ph][Co2(CO)6] [brown-
green solid, m.p. 124 ꢁC (dec.), Yield: 19% (20 mg,
0.03 mmol). Anal. Calc. for C39H28O6Co2Fe2: C, 56.97;
H, 3.43. Found: C, 57.46; H, 3.75%. IR (KBr disk) m
(CO) 2090s, 2054 vs, 2026vs cmꢀ1; mC„C 2172w cmꢀ1].
The isomer [FcC(CH3)2Fc0–C2–C„C–Ph][Co2(CO)6] of
FcC(CH3)2Fc0–C„CH (80 mg, 0.17 mmol), Ph–C„CH
(40 mg, 0.40 mmol) and CuCl (9 mg, 0.09 mmol) were dis-
solved in 8 ml pyridine. The mixture solution was stirred
for 3 h in air at 60 ꢁC. The solvent was removed under
reduced pressure. The resulting mixture was washed with
saturated NH4Cl solution and extracted with CH2Cl2.
The organic phase was incorporated and then dried using
the dehydrated MgSO4 and filtrated. The filtrate was con-
centrated and the residue was subjected to chromato-
graphic separation on the neutral alumina column
(2.0 · 30 cm). Elution with a mixture of hexane–benzene
(2:1, v/v) afforded a yellow band. The yellow crystal of
ligand L1 was obtained by recrystallizing from hexane–ben-
zene. Yield: 61% (56 mg, 0.10 mmol). m.p. 158–161 ꢁC.
Anal. Calc. for C33H28Fe2: C, 73.91; H, 5.26. Found: C,
73.67; H, 5.14%. IR (KBr disk) 3089 [Cp, mC–H]; 2976,
2930, 2863 [C(CH3)2, mC–H]; 2208, 2141 [C„C, mC„C];
1588, 1491, 1440 [C6H5, mC@C]; 1105, 999 [Cp, cC–H]; 818
[Cp, dC–H]; 755, 688 [C6H5, cC–H] cmꢀ1. 1H NMR (CDCl3,
d): 7.3–7.5 (m, 5H, C6H5), 4.0–4.4 (m, 17H, Cp), 1.5 [s, 6H,
C(CH3)2]. 13C NMR (CDCl3, d): 132.3, 128.8, 128.4, 122.2
(C6H5); 118.6, 102.8, 70.7, 70.2, 68.3, 67.3 (Cp); 82.5, 78.7,
74.8, 71.0 (–C„C–C„C–); 33.2, 30.2 [C(CH3)2]. MS (EI):
536 (M+).
1
complex 1: H NMR (CDCl3, d): 7.3–7.7 (m, 5H, C6H5),
3.9–4.5 (m, 17H, Cp), 1.5 [s, 6H, C(CH3)2]. 13C NMR
(CDCl3, d): 198.7 (CO); 129.2, 128.9, 113.6 (C6H5); 100.8,
91.1 (–C„C–C„C–); 65.8-72.3 (Cp); 30.3 [C(CH3)2]. MS
(FAB): 822 (M+).
2.5. Synthesis of complex [FcC(CH3)2Fc0–C„C–C„C–
Ph][Co2(CO)6]2 (2)
2.3. Synthesis of ligand Fc–C„C–C„C–Ph (L2)
Fc–C„CH (100 mg, 0.50 mmol), Ph–C„CH (50 mg,
1.00 mmol) and CuCl (12 mg, 0.12 mmol) were dissolved
in 20 ml pyridine. The mixture solution was stirred for
3 h in air at 60 ꢁC. The solvent was removed under
A benzene solution of Co2(CO)8 (77 mg, 0.22 mmol)
and ligand L1 (60 mg, 0.11 mmol) was stirred for 12 h at
room temperature. The solvent of the resulting mixture

N. Zhu et al. / Polyhedron 26 (2007) 981–988
983
was removed in vacuum. The residue was dissolved in a
2.7. Synthesis of complex [Fc–C„C–C„C–Ph]-
[Co2(CO)6]2 (4)
minimal amount of benzene and subjected to chromato-
graphic separation on a silica gel column (2.0 · 40 cm).
Elution with hexane–benzene (5:1,v/v) afforded a brown-
green band (2). The crystal of 2 was obtained by recrystal-
lizing from hexane at ꢀ20 ꢁC. Yield: 24% (29 mg,
0.03 mmol) m.p. 105 ꢁC (dec.). Anal. Calc. for C45H28O12-
Co4Fe2: C, 48.78; H, 2.55. Found: C, 48.31; H, 2.64%. IR
(KBr disk) m(CO) 2097s, 2077vs, 2054s, 2036vs, 2019vs
A benzene solution of Co2(CO)8 (220 mg, 0.64 mmol)
and ligand L2 (100 mg, 0.32 mmol) was stirred for 21 h at
room temperature. The solvent of the resulting mixture
was removed in vacuum. The residue was dissolved in a
minimal amount of benzene and subjected to chromato-
graphic separation on a silica gel column (2.0 · 40 cm). Elu-
tion with hexane–benzene (10:1, v/v) afforded a brown-
green band (4). The crystal of 4 was obtained by recrystal-
lizing from hexane at ꢀ20 ꢁC. The complex 4: Yield: 78%
(220 mg, 0.25 mmol). m.p. 135–138 ꢁC. Anal. Calc. for
C32H14O12Co4Fe: C, 43.58; H, 1.60. Found: C, 43.91; H,
1.68%. IR (KBr disk) m (CO) 2075s, 2053vs, 2023vs,
cmꢀ1 1H NMR (CDCl3, d): 7.3–7.5 (m, 5H, C6H5),
.
4.0–4.3 (m, 17H, Cp), 1.6 [s, 6H, C(CH3)2]. 13C NMR
(CDCl3, d): 198.8 (CO); 129.3, 128.7, 127.8 (C6H5);
65.8–72.3 (Cp); 30.5, 29.5 [C(CH3)2]. MS (FAB): 1108
(M+).
1
2010s, 2002s cmꢀ1. H NMR (CDCl3, d): 7.3–7.5 (m, 5H,
C6H5), 4.3–4.5 (m, 9H, Cp).13C NMR (CDCl3, d): 199.1
(CO), 138.4, 129.3, 128.6, 128.3 (C6H5), 88.3 (–C„C–
C„C–), 71.1, 69.6, 68.7 (Cp). MS (FAB): 882 (M+).
2.6. Synthesis of complex [Fc–C„C–C„C–Ph]-
[Co2(CO)6] (3)
A benzene solution of Co2(CO)8 (55 mg, 0.16 mmol)
and ligand L2 (50 mg, 0.16 mmol) was stirred for 3 h at
room temperature. The solvent of the resulting mixture
was removed in vacuum. The residue was dissolved in a
minimal amount of benzene and subjected to chromato-
graphic separation on a silica gel column (2.0 · 40 cm).
Elution with hexane–benzene (15:1, v/v) afforded a
brown-green band (3). The complex 3: Yield: 22%
(21 mg, 0.04 mmol). m.p. 83–85 ꢁC. Anal. Calc. for
C26H14O6Co2Fe: C, 52.39; H, 2.37. Found: C, 52.46; H,
2.44%. IR (KBr disk) m (CO) 2094s, 2058vs, 2038vs,
2.8. X-ray crystallography of compounds L1, L2, 2 and 4
The crystals of L1, L2, 2 and 4 were mounted on a glass
fiber, respectively. All measurements were made on the
Bruker SMART APEX CCD diffractometers with graphite
˚
monochromated Mo Ka (k = 0.71073 A) radiation. All
data were collected at 20 ꢁC using the u and x scan tech-
niques. All structures were solved by direct methods and
expanded using Fourier technique [25]. An absorption cor-
rection based on the SADABS was applied [26]. All non-
hydrogen atoms were refined by the full matrix least-
squares on F2. Hydrogen atoms were located and refined
by geometry method. The cell refinement, data collection
and reduction were done by Bruker SMART and SAINT [27].
2011vs cmꢀ1 1H NMR (CDCl3, d): 7.3–7.6 (m, 5H,
.
C6H5), 4.3–4.5 (m, 9H, Cp). 13C NMR (CDCl3, d):
198.7 (CO), 131.4, 128.5 (C6H5), 70.1, 69.8, 69.3 (Cp).
MS (CSI): 596 (M+).
(CO)
3 Co
Co (CO)3
Co2(CO)8
CH3
C
CH3
C
C
C
C
C
C
C
C
C
CH3
CH3
Fe
Fe
Fe
Fe
L1
1,isomer
CH3
C
C
C
C
C
Co2(CO)8
CH3
(CO)3Co
Co (CO)3
Fe
Fe
1, isomer
Co (CO)3
(CO)3 Co
C
CH3
C
(CO)
(CO)
3
3 Co Co
C
C
C
C
C
C
C
CH3
(CO)3 Co
Co (CO)3
Fe
Fe
(CO)3Co
by-product
Co (CO)3
2
(CO)
(CO)
3Co
C
Co
C
(CO)
Co
C
3Co
(CO)3
C
3
Co2(CO )8
C
C
C
C
C
C
C
C
(CO)3Co
4
Co (CO)3
Fe
Fe
Fe
L2
3
Scheme 1.

Table 1
Crystal data and structure refinement for L1, L2, 2 and 4
Identification code
L1
L2
2
4
Empirical formula
Formula weight
Temperature (K)
C
33H28Fe2
C20H14Fe
310.16
293(2)
0.71073
monoclinic
P2(1)/n
C45H28O12Co4Fe2
1108.09
293(2)
0.71073
monoclinic
P2(1)/n
C32H14O12Co4Fe
882.00
293(2)
0.71073
monoclinic
P2(1)/c
536.25
293(2)
0.71073
triclinic
˚
Wavelength (A)
Crystal system
Space group
Unit cell dimensions
ꢀ
P1
˚
a (A)
6.288(2)
6.2934(17)
12.816(3)
18.460(5)
90
90.498(4)
90
1488.9(7)
4
18.923(7)
9.572(4)
24.789(10)
90
103.770(6)
90
4361(3)
18.079(6)
10.746(3)
16.950(5)
90
101.415(4)
90
3227.7(17)
4
1.815
˚
b (A)
13.222(5)
15.440(5)
84.772(5)
83.430(5)
81.642(5)
1258.0(8)
2
1.416
1.173
556
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
3
˚
Volume (A )
Z
4
Dcalc (Mg/m3)
Absorption coefficient (mmꢀ1
F(000)
1.384
1.002
640
1.688
2.196
2216
)
2.515
1744
Crystal size (mm)
h Range (ꢁ)
0.35 · 0.15 · 0.10
1.56–25.01
7 6 h 6 7,
15 6 k 6 12, 18 6 l 6 16
5322
0.15 · 0.10 · 0.10
1.93–26.01
7 6 h 6 7,
15 6 k 6 15, 22 6 l 6 8
6727
0.30 · 0.15 · 0.10
1.22–26.01
23 6 h 6 23,
11 6 k 6 10, 30 6 l 6 24
19324
0.15 · 0.15 · 0.10
1.15–26.01
22 6 h 6 21,
9 6 k 6 13, 18 6 l 6 20
14012
Limiting indices
Reflections collected
Independent reflections (Rint
Completeness to h (%)
Maximum and
)
4377 (0.0168)
98.3
0.8917 and 0.6843
2929 (0.0635)
99.9
0.9065 and 0.8643
8564 (0.0732)
99.8
0.8103 and 0.5587
6313 (0.0334)
99.4
0.7870 and 0.7041
minimum transmission
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2r(I)]
R indices (all data)
4377/0/318
0.836
R1 = 0.0346, wR2 = 0.0638
R1 = 0.0569, wR2 = 0.0672
2929/0/190
0.964
R1 = 0.0519, wR2 = 0.0905
R1 = 0.1227, wR2 = 0.1111
8564/0/570
0.840
R1 = 0.0590, wR2 = 0.1303
R1 = 0.1488, wR2 = 0.1676
6313/0/442
1.003
R1 = 0.0341, wR2 = 0.0665
R1 = 0.0558, wR2 = 0.0783
Largest difference in
0.321 and ꢀ0.298
0.442 and ꢀ0.200
0.911 and ꢀ0.574
0.434 and ꢀ0.269
ꢀ3
˚
peak and hole (e A
)
Weighing scheme
calc. w ¼ 1=½r2ðF o2Þ
calc. w ¼ 1=½r2ðF o2Þ
calc. w ¼ 1=½r2ðF o2Þ
calc. w ¼ 1=½r2ðF o2Þ
2
2
2
2
þð0:0285PÞ þ 0:0000Pꢁ,
þð0:0430PÞ þ 0:0000Pꢁ,
þð0:0835PÞ þ 0:0000Pꢁ,
þð0:0289PÞ þ 0:9976Pꢁ,
P ¼ ðF 2o þ 2F 2c Þ=3
P ¼ ðF 2o þ 2F 2cÞ=3
P ¼ ðF 2o þ 2F 2c Þ=3
P ¼ ðF 2o þ 2F 2c Þ=3

N. Zhu et al. / Polyhedron 26 (2007) 981–988
985
The structure solution and refinement were performed by
SHELXSL97 [28].
3. Results and discussion
3.1. Synthesis and characterization of compounds L1, L2, 1,
2, 3 and 4
The reactions carried out in this work are summarized in
Scheme 1. A new ligand FcC(CH3)2Fc0–C„C–C„C–Ph
(L1) was synthesized by the cross coupling reaction of
FcC(CH3)2Fc0–C„CH and Ph–C„CH in the presence of
catalyst CuCl, and ligand Fc–C„C–C„C–Ph (L2) was
obtained by the similar route. Complexes [FcC(CH3)2-
Fc0–C„C–C„C–Ph][Co2(CO)6] (1) and [Fc–C„C–
C„C–Ph][Co2(CO)6] (3) were achieved by the reactions
of L1 and L2 with equal Co2(CO)8 under mild condition,
respectively, and complexes [FcC(CH3)2Fc0–C„C–C„C–
Ph][Co2(CO)6]2 (2) and [Fc–C„C–C„C–Ph]- [Co2(CO)6]2
(4) were provided by the reactions of L1 and L2 with excess
Co2(CO)8, respectively. By-product [Ph–C„C–C„C–
Ph][Co2(CO)6]2 is probably produced by the self-coupling
of the fragment –C„C–Ph of ligand FcC(CH3)2Fc0–
C„C–C„C–Ph and the reaction with Co2(CO)8. The
coordinated isomers of complex 1, [FcC(CH3)2Fc0–
C„C–C2–Ph][Co2(CO)6] and [FcC(CH3)2Fc0–C2–C„C–
Ph][Co2(CO)6] have successfully been separated by the col-
umn chromatography technique.
Fig. 1. Molecular structure of ligand L1.
Ligands L1 and L2 are yellow and air-stable crystal com-
pound which is soluble in both non-polar solvents such as
hexane, petroleum ether, benzene and polar solvents such
as diethylether and chloroform. Complexes 2 and 4 are
brown-green and air-stable crystal compound which their
solubility is similar to ligands L1 and L2 and complexes 1
and 3 are also brown-green but air-sensitive. By-product
[Ph–C„C–C„C–Ph][Co2(CO)6]2 is red air-stable crystal
compound and the coordinated isomers [FcC(CH3)2Fc0–
C„C–C2–Ph][Co2(CO)6] and [FcC(CH3)2Fc0–C2–C„C–
Ph][Co2(CO)6] are oil compound, which their solubility is
also similar to ligand L1.
Fig. 2. Molecular structure of complex 2.
The FTIR spectra in the region 2097–2002 cmꢀ1 confirm
that there is the coordinated Co2(CO)6 species and 1H and
13C NMR reflect that there are Fc, Ph, C„C, C(CH3)2
and CO groups in complexes 1, 2, 3 and 4. The structure
and composing of compounds L1, L2, 1, 2, 3 and 4 are fur-
ther proved by the data of their elemental analysis and MS.
The molecular structures of compounds L1, L2, 2 and 4
were determined by X-ray crystallography.
Fig. 3. Molecular structure of ligand L2.
The molecule of ligand L1 contains a butadiynyl chain,
of which terminals are phenyl and bisferrocenylpropane
groups, respectively (see Fig. 1). The bond distances
˚
˚
C(12)–C(13) (1.193 A) and C(14)–C(15) (1.200 A) show
3.2. Molecular structures of compounds L1, L2, 2 and 4
there are carbon–carbon triple bonds in L1. The shorter
˚
˚
C(9)–C(12) (1.436 A), C(13)–C(14) (1.370 A) and C(15)–
The molecular structures of compounds L1, L2, 2 and 4
were determined by X-ray single crystal analysis. Crystal
data and relevant structural parameters are enumerated
in Table 1.The structures with the atom numbering scheme
are shown in Figs. 1–4, respectively, and the selected bond
lengths and angles for L1, L2, 2 and 4 are listed in Table 2.
˚
C(16) (1.432 A) bond distances are the results of electron
delocalization of the C4 diyne chain, phenyl unit and cyclo-
pentadiene ring. The data of the bond angles [C(9)–C(12)–
C(13), 174.6ꢁ; C(12)–C(13)–C(14), 177.6ꢁ; C(13)–C(14)–
C(15), 178.0ꢁ; C(14)–C(15)–C(16), 177.0ꢁ] demonstrate

986
N. Zhu et al. / Polyhedron 26 (2007) 981–988
C(6) in L1 because of the influence of large bulk of ferroce-
nyl moieties.
In complex 2 the bond angle data [C(9)–C(12)–C(13),
143.4ꢁ; C(12)–C(13)–C(14), 145.8ꢁ; C(13)–C(14)–C(15),
142.9ꢁ; C(14)–C(15)–C(16), 141.4ꢁ] and the torsion angle
[C(12)–C(13)–C(14)–C(15), ꢀ39ꢁ] demonstrate the con-
struction of L1 is altered from the linear to nonlinear struc-
ture while L1 was coordinated to Co2(CO)6 units. It is
noteworthy that Co2(CO)6 units are coordinated to the
alkyne bond in a cis configuration and two terminal groups
(phenyl and bisferrocenylpropane) are also in a cis position
(see Fig. 2). Because of a large substituted group bisferroce-
nylpropane, the molecular structure of 2 is quite different
from 4.
In L1 the distance of Fe atom to the plane of cyclopent-
˚
adiene ring [Fe1 to plane (1) C(1)C(2)C(3)C(4)C(5), 1.65 A;
˚
Fe1 to plane (2) C(24)C(25)C(26)C(27)C(28), 1.65 A; Fe2 to
˚
plane (3) C(7)C(8)C(9)C(10)C(11), 1.64 A; Fe2 to plane (4)
˚
C(29)C(30)C(31)C(32)C(33), 1.66 A] is nearly equal. The
Fig. 4. Molecular structure of complex 4.
dihedral angles between plane (1) C(1)C(2)C(3)C(4)C(5)
and plane (2) C(24)C(25)C(26)C(27)C(28) (3.59ꢁ) and
between plane (3) C(7)C(8)C(9)C(10)C(11) and plane (4)
C(29)C(30)C(31)C(32)C(33) (3.57ꢁ) in L1 reveal that two
Cp planes in Fc or Fc0 deviate from parallel because of dif-
ferent substituted Cp ring and steric interaction. It is inter-
esting to note that the dihedral angle between plane (2) and
plane (3) is nearly perpendicular(88.98ꢁ) as a result of the
steric influence. In 2 the distance of Fe atom to the plane
the carbon chain C(9) C(12) C(13) C(14) C(15) C(16) is
nearly linear structure. The bond angle C(22)–C(6)–C(23)
(108.5ꢁ) is close to 109ꢁ and other bond angles [C(5)–
C(6)–C(7), 105.3ꢁ; C(5)–C(6)–C(22), 110.8ꢁ; C(5)–C(6)–
C(23), 111.0ꢁ; C(7)–C(6)–C(22), 111.4ꢁ; C(7)–C(6)–C(23),
110.0ꢁ] clearly deviate from 109ꢁ around the sp3-hybridized
Table 2
˚
Selected bond lengths (A) and angles (ꢁ) for L1, L2, 2 and 4
Bond lengths
Bond angles
L1
C(1)–C(5)
C(5)–C(6)
C(6)–C(22)
C(8)–C(9)
C(9)–C(12)
1.414(4)
1.523(3)
1.529(3)
1.434(3)
1.436(4)
C(12)–C(13)
C(13)–C(14)
C(14)–C(15)
C(15)–C(16)
C(16)–C(17)
1.193(4)
1.370(4)
1.200(4)
1.432(4)
1.380(4)
C(1)–C(5)–C(6)
C(5)–C(6)–C(7)
C(6)–C(7)–C(8)
C(8)–C(9)–C(12)
C(9)–C(12)–C(13)
127.2(2)
105.3(2)
126.5(2)
127.4(3)
174.6(3)
C(12)–C(13)–C(14)
C(13)–C(14)–C(15)
C(14)–C(15)–C(16)
C(15)–C(16)–C(17)
C(15)–C(16)–C(21)
177.6(3)
178.0(3)
177.0(3)
119.8(3)
121.5(3)
L2
C(6)–C(10)
C(10)–C(11)
C(11)–C(12)
1.430(5)
1.423(6)
1.191(5)
C(12)–C(13)
C(13)–C(14)
C(14)–C(15)
1.385(6)
1.185(5)
1.443(6)
C(6)–C(10)–C(11)
C(10)–C(11)–C(12)
C(11)–C(12)–C(13)
127.9(4)
178.3(4)
176.8(4)
C(12)–C(13)–C(14)
C(13)–C(14)–C(15)
C(14)–C(15)–C(16)
177.5(4)
175.9(4)
120.6(4)
2
C(9)–C(12)
C(12)–C(13)
C(13)–C(14)
C(14)–C(15)
C(15)–C(16)
C(16)–C(17)
Co(1)–Co(2)
Co(1)–C(12)
1.441(9)
1.349(9)
1.429(9)
1.350(9)
1.448(9)
1.350(1)
2.457(2)
1.962(6)
Co(1)–C(13)
Co(2)–Co(12)
Co(2)–C(13)
Co(3)–Co(4)
Co(3)–C(14)
Co(3)–C(15)
Co(4)–C(14)
Co(4)–C(15)
1.981(7)
1.973(7)
1.981(7)
2.449(2)
1.970(7)
1.952(6)
1.982(7)
1.961(7)
C(8)–C(9)–C(12)
129.5(7)
143.4(6)
145.8(6)
142.9(6)
141.4(6)
122.4(7)
70.7(4)
Co(2)–C(12)–C(13)
Co(2)–C(13)–C(12)
Co(1)–Co(2)–C(12)
C(12)–Co(1)–Co(2)
Co(3)–C(14)–C(15)
Co(3)–C(15)–C(14)
Co(4)–C(14)–C(15)
Co(4)–C(15)–C(14)
70.4(4)
69.7(4)
51.2(2)
51.6(2)
69.2(4)
70.6(4)
69.2(4)
70.8(4)
C(9)–C(12)–C(13)
C(12)–C(13)–C(14)
C(13)–C(14)–C(15)
C(14)–C(15)–C(16)
C(15)–C(16)–C(17)
Co(1)–C(12)–C(13)
Co(1)–C(13)–C(12)
69.3(4)
4
Co(1)–Co(2)
Co(1)–C(11)
Co(1)–C(12)
Co(2)–C(11)
Co(2)–C(12)
Co(3)–Co(4)
Co(3)–C(13)
2.459(9)
1.954(3)
1.996(3)
1.985(3)
1.996(3)
2.460(9)
1.978(3)
Co(4)–C(14)
C(9)–C(10)
C(10)–C(11)
C(11)–C(12)
C(12)–C(13)
C(13)–C(14)
C(14)–C(15)
1.942(3)
1.427(5)
1.448(4)
1.346(4)
1.431(4)
1.343(4)
1.464(4)
C(11)–Co(1)–Co(2)
C(11)–Co(2)–Co(1)
C(12)–Co(1)–Co(2)
C(12)–Co(2)–Co(1)
C(13)–Co(3)–Co(4)
C(13)–Co(4)–Co(3)
C(14)–Co(3)–Co(4)
51.95(1)
50.79(9)
51.98(9)
51.98(9)
52.03(9)
51.45(9)
50.46(1)
C(14)–Co(4)–Co(3)
C(9)–C(10)– C(11)
C(10)–C(11)–C(12)
C(11)–C(12)–C(13)
C(12)–C(13)–C(14)
C(13)–C(14)–C(15)
C(14)–C(15)–C(16)
51.86(1)
125.7(3)
147.4(3)
145.8(3)
143.5(3)
141.9(3)
119.6(3)

N. Zhu et al. / Polyhedron 26 (2007) 981–988
987
˚
of cyclopentadiene ring [Fe(1) to plane(1), 3.32 A; Fe(1) to
The crystal structures of compounds L1, L2, 2 and 4 have
been determined by X-ray single crystal diffraction. The
syntheses and structures of compounds L1, 1, 2, 3 and 4
and the structure of ligand L2 are firstly reported. The
molecular structure data show the butadiynyl groups of
ligands L1 and L2 are nearly linear structure and the coor-
dinated butadiynyl groups in the complexes 2 and 4 have
deviated from linear structure of ligands L1 and L2.
˚
˚
plane (2), 6.86 A; Fe (2) to plane (3), 0.65A; Fe (2) to plane
(4), 2.57A] is quite different from L1 because of the coordi-
˚
nation effect of Co2 core with diyne. The dihedral angles
between plane (1) and plane (2) (5.27ꢁ) and between plane
(3) and plane (4) (2.12ꢁ) demonstrate that two Cp planes in
2 also deviate from parallel like L1 but the dihedral angle
between plane (2) and plane (3) alters from 88.98ꢁ to
67.11ꢁ as a result of the diyne coordinated to Co2 core.
The molecule of ligand L2 also contains a butadiynyl
chain but its terminals are phenyl and ferrocenyl group,
respectively (see Fig. 3). The relevant bond distances in
L2 are similar to L1, which also reveal the electron delocal-
ization among C4 diyne chain, phenyl and cyclopentadiene
ring. The data of bond angles (see Table 2) demonstrate the
carbon chain C(10) C(11) C(12) C(13) C(14) C(15) of L2 is
nearly linear structure.
Acknowledgments
We are grateful to the Startup Foundation of China
Scholar Abroad, the Inner Mongolia Talent Foundation
and the Inner Mongolia Science Foundation for financial
support of this work.
Appendix A. Supplementary material
The –C„C–C„C– acetylenic linkage in complex 4 is
nonlinear, which is proved by the bond angles [C(10)–
C(11)–C(12), 147.4ꢁ; C(11)–C(12)–C(13), 145.8ꢁ; C(12)–
C(13)–C(14), 143.5ꢁ; C(13)–C(14)–C(15), 141.9ꢁ] and the
torsion angle [C(11)–C(12)–C(13)–C(14), 159.3ꢁ], contrast-
ing sharply with the linear –C„C–C„C– carbon chain of
L2. In 4 the two C2Co2 units are coordinated to the C4
diyne chain in a trans configuration. The outer C atoms
of the diyne chain, C(11) and C(14), carry ferrocenyl and
phenyl substituents also orientated trans to each other
(see Fig. 4). The molecular structure of L2 and 4 are similar
to compounds Fc–C„C–C„C–Fc and Fc–C„C–C„C–
Fc [Co2(CO)6]2, respectively [11,29,30].
CCDC 297322, 297319, 297324 and 297321 contain the
supplementary crystallographic data for L1, L2, 2 and 4.
These data can be obtained free of charge via http://
www.ccdc.cam.ac.uk/conts/retrieving.html, or from the
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or
e-mail: deposit@ccdc.cam.ac.uk. Supplementary data asso-
ciated with this article can be found, in the online version,
at doi:10.1016/j.poly.2006.09.044.
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