Transition-metal complexes based on the 1,3,5-triethynyl benzene linking unit

Article abstract of DOI:10.1002/zaac.201000243

The synthesis of a unique series of heteromultinuclear transition metal compounds is reported. Complexes 1-I-3-Br-5-(FcC≡C)-C₆H ₃ (4), 1-Br-3-(bpy-C≡C)-5-(FcC≡C)-C₆H ₃ (6), 1,3-(bpy-C≡C)₂-5-(FcC≡C)-C

Full text of DOI:10.1002/zaac.201000243

ARTICLE
DOI: 10.1002/zaac.201000243
Transition-Metal Complexes Based on the 1,3,5-Triethynyl Benzene Linking
Unit
Rico Packheiser,[a] Tobias Rüffer,[a] Petra Ecorchard,[a] and Heinrich Lang*[a]
Keywords: Heteromultimetallics; Solid-state structures; Transition metals; Acetylides; Ferrocene
Abstract. The synthesis of a unique series of heteromultinuclear tran- synthesis methodologies including metathesis, desilylation, dehydroha-
sition metal compounds is reported. Complexes 1-I-3-Br-5-(FcC≡C)- logenation, and carbon–carbon cross-coupling reactions. In these com-
C6H3 (4), 1-Br-3-(bpy-C≡C)-5-(FcC≡C)-C6H3 (6), 1,3-(bpy-C≡C)2-5- plexes the corresponding metal atoms are connected by carbon-rich
(FcC≡C)-C6H3 (7), 1-(XC≡C)-3-(bpy-C≡C)-5-(FcC≡C)-C6H3 (8, X = bridging units comprising 1,3-diethynyl-, 1,3,5-triethynylbenzene and
SiMe3; 9, X = H), 1-(HC≡C)-3-[(CO)3ClRe(bpy-C≡C)]-5-(FcC≡C)- bipyridyl units. They were characterized by elemental analysis, IR and
C6H3 (11), 1-[(Ph3P)AuC≡C]-3-[(CO)3ClRe(bpy-C≡C)]-5-(FcC≡C)- NMR spectroscopy, and partly by ESI-TOF mass spectrometry.
C6H3 (13), 1-[(Ph3P)AuC≡C]-3-(bpy-C≡C)-5-(FcC≡C)-C6H3 (14), [1- The structures of 4 and 11 in the solid state are reported. Both molecu-
[(Ph3PAuC≡C]-3-[{[Ti](C≡CSiMe3)2}Cu(bpy-C≡C)]-5-(FcC≡C)-
les are characterized by the central benzene core bridging the individ-
C6H3]PF6 (16), and [1,3-[(tBu2bpy)2Ru(bpy-C≡C)]2-5-(FcC≡C)- ual transition metal complex fragments. The corresponding acetylide
C6H3](PF6)4 (18) (Fc = (η5-C5H4)(η5-C5H5)Fe, bpy = 2,2'-bipyridiyl- entities are, as typical, found in a linear arrangement with representa-
5-yl, [Ti] = (η5-C5H4SiMe3)2Ti) were prepared by using consecutive tive M–C, C–CC≡C and C≡C bond lengths.
the electrochemical behavior, UV/Vis/NIR characteristics and
Introduction
EPR analysis of in-situ generated associated radical cations
The synthesis of carbon-rich acetylide-containing molecules
were studied [6–8].
opens new avenues of fundamental and technological research
As an extension of our previous work in the field of hetero-
at the interface between chemistry and materials science. Unu-
multimetallic chemistry, in which we connected different early
sual structures, high stability and useful electronic properties
and late transition metal atoms with carbon-rich organic and
are some of the desirable fundamental characteristics of such
inorganic bridging units, we here focus on some further
systems, which have captured much attention during the last
straightforward synthesis methods for the preparation and
years [1]. In this context, interest centers on those compounds
characterization of diverse unsymmetrical compounds featur-
that contain redox-active metal building blocks next to the car-
ing the transition metals titanium, rhenium, iron, ruthenium,
bon-rich structural units, among which the ferrocenyl moiety
copper, and gold, and comprising 1,3,5-triethynylbenzene and
has been most studied. The ferrocenyl group is, for example,
2,2'-bipyridiyl-5-yl (= bpy) organic connecting units. The
robust, represents a one-electron reservoir and can undergo re-
structure of two molecules in the solid state is discussed as
versible redox processes [2]. Very recently, ferrocenyl entities,
well.
(η5-C5H4)(η5-C5H5)Fe, have been successfully applied in the
synthesis of heteromultimetallic transition metal complexes, in
which the metal atoms are bridged by carbon-rich connectivi-
ties [3]. Whereas homo- and heterobimetallic complexes with
carbon-rich organic and/or inorganic connecting units were de-
signed and synthesized, and their chemical and physical prop-
erties were intensively studied [4, 5], only less is known about
organometallics in which more than three different metals are
linked by organic π-conjugated bridging ligands [3]. Such mol-
ecules are of great interest, due to their extended organic π
system which can provide remarkable applications and hence,
Results and Discussion
In terms of synthesizing heteromultimetallic transition metal
complexes based on the 1,3,5-triethynylbenzene core, we
chose ferrocenyl-functionalized 1-I-3-Br-5-(FcC≡C)-C6H3 (4)
as suitable key starting material. The organometallic com-
pound 4 was synthesized by subsequent treatment of 1-I-3,5-
Br2-C6H3 (1) with FcC≡CH (2) under Sonogashira cross-coup-
ling conditions to produce 1,3-Br2-5-FcC≡C-C6H3 (3), which
on Br–I exchange eventually resulted in the formation of 4
(Scheme 1) [7].
The diethynyl-substituted compound 1-Br-3-(bpy-C≡C)-5-
(FcC≡C)-C6H3 (6) was accessible by the reaction of 4 with
one equivalent of 5-ethynyl-2,2'-bipyridine (5) under typical
Sonogashira carbon–carbon cross-coupling conditions (diiso-
propylamine, 40 °C), whereby the more reactive aryl–iodo
* Prof. Dr. H. Lang
Fax: +49-371-531-21219
E-Mail: heinrich.lang@chemie.tu-chemnitz.de
[a] Technische Universität
Institut für Chemie, Anorganische Chemie
Straße der Nationen 62
09111 Chemnitz, Germany
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R. Packheiser, T. Rüffer, P. Ecorchard, H. Lang
ARTICLE
Scheme 1. Consecutive reaction sequence for the synthesis of 9.
bond allowed the preferential introduction of one 5-ethynyl- lytic amounts of [CuI] complex 13, in which the three complex
2,2'-bipyridyl moiety (Scheme 1, Experimental Section). After
appropriate work-up, mononuclear compound 6 was isolated
as an orange solid in 78 % yield. As side product the corre-
sponding disubstituted molecule 1,3-(bpy-C≡C)2-5-(FcC≡C)-
C6H3 (7) could be isolated in a yield of 7 % (Experimental
Section). The exchange of one bromide substituent by the more
reactive iodide in 3 was necessary to obtain complex 6 as ma-
jor product. If 3 reacted under similar reaction conditions with
bpyC≡CH (5), a mixture of 6 and 7 was obtained. Complex 6
reacted further with an excess of trimethylsilylacetylene under
similar reaction conditions whereby the reaction mixture had
to be heated to 80 °C for completion and hence, forming 1-
(Me3SiC≡C)-3-(bpy-C≡C)-5-(FcC≡C)-C6H3 (8). Desilylation
of 8 with [nBu4N]F in tetrahydrofuran at ambient temperature
finally gave 1-(HC≡C)-3-(bpy-C≡C)-5-(FcC≡C)-C6H3 (9) as a
yellow solid (Scheme 1).
fragments Fc, (bpy)Re(CO)3Cl, and (Ph3P)Au are connected
by a 1,3,5-triethynylbenzene core (Scheme 2).
Even the synthesis of a heterotetrametallic complex featuring
titanium, iron, copper, and gold metal atoms was possible by
starting from 9. In this respect, the heterobimetallic complex
1-[(Ph3P)AuC≡C]-3-(bpy-C≡C)-5-(FcC≡C)-C6H3 (14) was
prepared using a mixture of tetrahydrofuran-diethylamine in
1:1 ratio at 25 °C (Scheme 2). It was necessary to add a cata-
lytic amount of [CuI] to the reaction medium for completion
of the reaction [8]. The last step in the synthesis of [1-
[(Ph3P)AuC≡C]-3-[{[Ti](C≡CSiMe3)2}Cu(bpy-C≡C)]-5-
(FcC≡C)-C6H3]PF6 (16) ([Ti] = (η5-C5H4SiMe3)2Ti) included
the addition of the heterobimetallic organometallic π-tweezed
molecule [{[Ti](μ-σ,π-C≡CSiMe3)2}Cu(N≡CMe)]PF6 (15) to
14. On replacement of the only weakly-bonded acetonitrile by
the 2,2'-bipyridyl ligand, the heterotetrametallic complex 16
was obtained as a red solid material in good yield after appro-
priate work-up (Scheme 2, Experimental Section).
With its different functionalities, the organometallic com-
pound 9 was used as starting material for the synthesis of
higher nuclear transition metal complexes featuring up to four
different metal atoms as outlined in Scheme 2.
The synthesis of
[(tBu2bpy)2Ru(bpy-C≡C)]2-5-(FcC≡C)-C6H3](PF6)4
a
trimetallic FeRu2 species, [1,3-
(18)
The synthesis of 1-[(Ph3P)AuC≡C]-3-[(CO)3ClRe(bpy-
C≡C)]-5-(FcC≡C)-C6H3 (13) (Scheme 2) includes following
(tBu2bpy = 4,4'-di-tert-butyl-2,2'-bipyridyl) was possible by
the reaction of 1,3-(bpy-C≡C)2-5-(FcC≡C)-C6H3 (7) with two
equivalents of [(tBu2bpy)2RuCl2] (17) in boiling ethanol (Re-
action 1). After 20 hours and addition of a aqueous solution of
[H4N]PF6, the ionic compound 18 could be isolated in 66 %
steps: (i) treatment of
9 with equimolar amounts of
[Re(CO)5Cl] (10) in toluene and heating the reaction medium
for 8 hours to 60 °C gave 1-(HC≡C)-3-[(CO)3ClRe(bpy-
C≡C)]-5-(FcC≡C)-C6H3 (11), which in the next step (ii) af-
forded on addition of [(Ph3P)AuCl] (12) in presence of cata- yield as a red material.
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Z. Anorg. Allg. Chem. 2010, 2607–2616

Transition-Metal Complexes with the 1,3,5-Triethynyl Benzene Linking Unit
Scheme 2. Synthesis of heterometallic 13 and 16 using 9 as key starting material.
(1)
All new synthesized multimetallic transition metal com-
The IR spectra of all compounds are characterized by very
plexes are stable both in solid state and solution, with excep- dominant νC≡C vibrations of the organometallic M–C≡CR (M =
tion of 16. This molecule slowly decomposes in solution over Ti, Au, Fc; R = C6H3, SiMe3) and the organic X–C≡C–C6H3
prolonged time on precipitation of non-soluble materials in (X = H, bpy, C5H4) units (Experimental Section). These vibra-
common organic solvents.
tions are found in the range of 2157–2214 cm–1 for the organic
The identities of 4, 6–9, 11, 13, 14, 16, and 18 were con- moieties, whereas for the metal acetylide fragments typical ab-
firmed by elemental analysis, IR, H, 13C{1H}, 31P{1H} NMR sorptions are observed at 2115 (AuC≡C) [9] and 1924 cm–1
1
spectroscopy, and partly by ESI-TOF mass spectrometry. The (TiC≡C) [10], respectively. For the HC≡C group present in 9
structure of complexes 4 and 11, respectively, in the solid state an additional strong absorption band is found at 3290 cm–1.
was additionally determined by single-crystal X-ray structure Furthermore, in the IR spectra of the corresponding metal–
analysis, thus confirming the structural assignment made from carbonyl molecules 11 and 13, the CO stretching vibrations are
spectroscopic characterization.
very diagnostic and represent a useful monitoring tool along
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R. Packheiser, T. Rüffer, P. Ecorchard, H. Lang
ARTICLE
with the appearance and disappearance of the νH–C≡C vibration Figure 2 (4) and Figure 3, Figure 4, and Figure 5 (11) together
(complex 11 vs. 13). For 11 and 13 three (11: 1894, 1914, and with selected bond lengths (in Å) and bond angles (in °). The
2022 cm–1; 13: 1896, 1915, and 2021 cm–1) very strong νCO crystallographic data are summarized in Table 1 (Experimental
bands are observed, which is typical for this type of species Section).
[11].
The consecutive formation of the multimetallic assemblies
from 3 and 4 is also confirmed by 1H NMR spectroscopy (Ex-
perimental Section). Characteristic for all compounds is the
appearance of typical ferrocenyl signals at ca. 4.25 ppm (sin-
glet) for the C5H5 ring protons and between 4.2–4.6 ppm
(pseudo-triplets) for the C5H4 protons with a JHH coupling con-
stant of ca. 1.9 Hz (Experimental Section). The titanium-
bonded cyclopentadienyl ligands in 16 are observed between
6.2–6.3 ppm as multiplet differing from the starting material
Figure 1. The molecular solid-state structure (ORTEP diagram, 50 %
probability level) of 4 with the atom numbering scheme. Hydrogen
15, where pseudo-triplets are characteristic. [12] The 1H NMR
atoms are omitted for clarity. Selected bond lengths /Å and bond an-
gles /°: Fe1–D1 1.644(4), Fe1–D2 1.654(4), C11–C12 1.206(12), C17–
Br1 1.947(9), C15–I1 2.031(8); C1–C11–C12 178.6(8), C11–C15–C13
178.4(8). D1 = centroid of C1–C5, D2 = centroid of C6–C10. Standard
uncertainties of the last significant digit(s) are shown in parentheses.
spectrum of 9 consists of a singlet at 3.14 ppm, which can be
assigned to the acetylenic proton. The bpy, C6H3, and C6H5
groups give typical resonances with the anticipated chemical
shifts and coupling patterns (Experimental Section). For exam-
ple, the aryl protons of the central phenylene ring were found
as three separated pseudo-triplets in the range of 7.4–7.8 ppm,
which show up-field shifts upon coordination of the alkynyl
units to a transition metal fragment (Experimental Section).
Most significant for 8 is the appearance of a resonance signal
at 0.26 ppm for the trimethylsilyl group. In this context, most
diagnostic for the formation of 16 is the high-field shift
(–0.48 ppm) of the Me3SiC≡C protons in comparison to 15
upon coordination of the bipyridyl entity to the organometallic
π-tweezed copper(I) atom, which can be explained by the ring
current of the chelating bipyridyl ligand [12, 13]. In addition,
as a result of the different chemical environment, the spectrum
of 16 reveals two well separated singlet signals at 0.28 and
0.30 ppm for the cyclopentadienyl-bonded Me3Si units (Exper-
imental Section). Similar observations were made in the
13C{1H} NMR spectra of the complexes described above.
The 31P{1H} NMR spectra of the (Ph3P)Au-containing mole-
cules 13, 14, and 16 show a singlet at ca. 41.5 ppm, which is
indicative of similar phosphane environments. Compared to
Figure 2. Graphical representation of the π–π-interactions of molecu-
the starting material [(Ph3P)AuCl] (12) (33.8 ppm [14]), a shift les of 4 in the solid state giving rise to the formation of 1D chains
along the crystallographic a-axis. Dotted lines refer to the shortest
to lower field is observed, which is typical for exchanging the
(3.480 Å) and dashed lines to the longest C–C contacts (3.561 Å) of
gold(I)-bonded chloride ion by an acetylide unit [9]. The non-
interacting cyclopentadienyl and phenyl rings with ∠ giving the inter-
coordinating PF6– ion in 16 gives rise to a septet at –145.1 ppm
planar angle. Labels ‘A’ to ‘D’ refer to the 1st–4th symmetry generated
1
with JPF = 713 Hz.
molecules of 4. Hydrogen atoms are omitted for clarity.
For multimetallic complexes 13 and 16 electrospray ioniza-
tion mass spectrometric investigations indicated the presence
of the appropriate molecular ions [M + H]+ (m/z 1253.4, 13),
[M – PF6]+ (m/z 1525.3, 16) with characteristic isotope distri-
bution patterns. Characteristic for 18 is the molecular ion [M –
4PF6]4+ (m/z 479.2) and the formation of fragments such as
[M – 4PF6 – Ru(tBu2bpy)2]2+ (m/z 639.6) (Experimental Sec-
tion).
Additionally, the molecular structures of 4 and 11 in the solid
state were determined by single-crystal X-ray diffraction. Sin-
gle crystals could be obtained by slow diffusion of n-hexane
into a chloroform solution containing either 4 or 11 at ambient
Both complexes 4 and 11 crystallize in the monoclinic space
group P21/n. From Figure 1 and Figure 3 it can be seen that
the structures of 4 and 11 are essentially similar as far as the
molecule backbone is concerned.
As typical for other ferrocenyl complexes, the Fe1–D1 and
Fe1–D2 separations in 4 and 11 are found to be in the range
1.640(4) and 1.654(4) Å [15]. The two cyclopentadienyl li-
gands are thereby rotated by 0.1(6)° (4) and 2.5(7)° (11) with
respect to each other, which verifies an almost eclipsed confor-
mation. The Fc-C≡C–, ((CO)3ClRe)bpy-C≡C–, and HC≡C–
acetylide units are, as expected, linear with typical C≡C sepa-
temperature. The perspective drawings with the atomic num- rations (Figure 1 and Figure 3). The bond lengths and bond
bering scheme of these molecules are shown in Figure 1 and angles for all the other groups agree well with those reported
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Transition-Metal Complexes with the 1,3,5-Triethynyl Benzene Linking Unit
Figure 3. The molecular solid-state structure (ORTEP diagram, 50 %
probability level) of 11 with the atom numbering scheme. Hydrogen
atoms are omitted for clarity. Selected bond lengths /Å and bond an-
gles /°: Fe1–D1 1.646(4), Fe1–D2 1.640(4), C11–C12 1.176(9), C19–
C20 1.188(11), C21–C22 1.212(10), Re1–N1 2.166(5), Re1–N2
2.184(6), Re1–Cl1 2.471(2), Re1–C33 1.904(9), Re1–C34 1.935(8),
Re1–C35 1.917(9), C33–O1 1.171(9), C34–O2 1.120(8), C35–O3
1.156(9); C1–C11–C12 174.3(8), C11–C12–C13 178.0(9), C17–C19–
C20 173.9(10), C15–C21–C22 177.5(8), C21–C22–C24 177.8(9), N1–
Re1–N2 74.8(2), C33–Re1–C35 89.1(3), C34–Re1–C11 176.5(2).
D1 = centroid of C1–C5, D2 = centroid of C6–C10. Standard uncer-
tainties of the last significant digit(s) are shown in parentheses.
Figure 5. Graphical illustration of the alignment of 1D chains formed
by 11 in the solid state with respect to the unit cell.
tions were made for other bpy-containing rhenium transition
metal complexes, including 1-[(tBu2bpy)(CO)3ReC≡C]-3,5-
(HC≡C)2-C6H3 [1s].
Furthermore, molecule 11 forms in the solid state a 1D chain
set up by π–π interactions among the pyridyl and phenyl rings
as it can be seen from Figure 4 and Figure 5. The shortest
distances are thereby 3.339 Å, which represents a quite strong
interaction [16].
Conclusions
Figure 4. Graphical illustration of the repeating unit of the 1D chains
formed by 11 in the solid state. Labels ‘A’ and ‘B’ refer to a 1st and a
2nd symmetry generated molecule of 11. Dotted lines indicate interac-
tions of carbon atoms of 11 and 11A, whereas the dashed lines repre-
senting the longest (3.427 Å) and open lines representing the shortest
(3.367 Å) distances. 11A/11B: Dashed lines the longest (3.558 Å) and
open lines the shortest (3.339 Å) distances.
A novel series of mono-, heterobi-, -tri- and even -tetrametallic
transition metal complexes based on the 1,3,5-triethynyl benzene
core was successfully synthesized using different consecutive
synthesis methodologies including metathesis, desilylation, dehy-
drohalogenation, and carbon–carbon cross-coupling reactions. In
the thus formed organometallic molecules 1-I-3-Br-5-(FcC≡C)-
C6H3, 1-Br-3-(bpyC≡C)-5-(FcC≡C)-C6H3, 1,3-(bpyC≡C)2-5-
elsewhere, and therefore it is not necessary to discuss them (FcC≡C)-C6H3, 1-(XC≡C)-3-(bpyC≡C)-5-(FcC≡C)-C6H3 (X = H,
separately [11, 15]. SiMe3), 1-(HC≡C)-3-[(CO)3ClRe(bpy-C≡C)]-5-(FcC≡C)-C6H3,
Molecule 4 has in the solid state π–π interactions between 1-[(Ph3P)AuC≡C]-3-[(CO)3ClRe(bpyC≡C)]-5-(FcC≡C)-C6H3,
the C5H5 ring and the C6H3 ring of the next molecule. This 1-[(Ph3P)AuC≡C]-3-(bpyC≡C)-5-(FcC≡C)-C6H3, [1-[(Ph3-
gives rise to the formation of 1D chains along the crystallo- PAuC≡C]-3-[{[Ti](C≡CSiMe3)2}Cu(bpy-C≡C)]-5-(FcC≡C)-
graphic a axis (Figure 2).
C6H3]PF6, and [1,3-[(tBu2bpy)2Ru(bpy-C≡C)]2-5-(FcC≡C)-
Most obvious, the structure of 11 in the solid state shows a C6H3](PF6)4 (Fc = (η5-C5H4)(η5-C5H5)Fe, bpy = 2,2'-bipyridiyl-
somewhat distorted octahedral arrangement around Re1 with 5-yl, tBu2bpy = 4,4'-di-tert-butyl-2,2'-bipyridyl, [Ti] = (η5-
three carbonyl ligands, arranged in a facial fashion. The N1– C5H4SiMe3)2Ti), the corresponding transition metal atoms are
Re1–N2 angle at 74.8(2)° is significantly less than 90°, as re- connected by a π-conjugated triethynyl benzene backbone and
quired by the bite distance exerted by the steric demand of the bipyridyl-5-yl ligands. The X-ray crystal structure analysis of
chelating bipyridyl building block (Figure 3). Similar observa- two compounds was also determined showing the characteristic
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R. Packheiser, T. Rüffer, P. Ecorchard, H. Lang
ARTICLE
Table 1. Crystal and Intensity Collection Data for 4 and 11.
4
11
Empirical formula
Formula weight
Temperature /K
Wavelength /Å
Crystal system
Space group
a /Å
C18H12Cl2BrFeI
490.94
C36H22Cl3FeN2O3Re
878.96
100(2)
110(2)
0.71073
monoclinic
P21/n
0.71073
monoclinic
P21/n
9.6235(6)
13.7445(9)
11.9791(8)
94.295(5)
1580.03(18)
2.064
14.0324(9)
7.5197(6)
32.398(2)
100.613(5)
3360.2(4)
1.737
b /Å
c /Å
β /°
V /Å3
ρcalc /g·cm–3
F(000)
936
1712
Crystal dimensions /mm
Z
0.6 × 0.4 × 0.1
4
0.1 × 0.05 × 0.03
4
Max., min. transmission
Absorption coefficient (μ /mm–1)
Scan range (°)
Index ranges
1.29694, 0.61021
5.426
1.00000, 0.84325
4.308
3.01 to 26.08
–10 ≤ h ≤ 11
–16 ≤ k ≤ 16
–13 ≤ l ≤ 14
7503
2.95 to 26.00
–17 ≤ h ≤ 15
–9 ≤ k ≤ 9
–39 ≤ l ≤ 39
25110
Total reflections
Unique reflections
3072
0.0216
6582
0.0720
R(int)
Data/restraints/parameters
Goodness-of-fit on F2
R1,a) wR2a) [I ≥ 2σ (I)]
R1,a) wR2a) (all data)
Max., min. peak in final Fourier map (e·Å–3)
3072 / 0 / 190
1.075
6582 / 58 / 445
1.030
0.0514, 0.1628
0.0558, 0.1658
3.066, –2.747
0.0490, 0.0732
0.1077, 0.0883
1.403, –0.847
a) R1 = [Σ(||Fo|–|Fc|)/Σ|Fo|); wR2 = [Σ(w(Fo –Fc ) )/Σ(wFo )]1/2. S = [Σw(Fo –Fc ) ]/(n – p)1/2. n = number of reflections, p = parameters used.
2
2 2
4
2
2 2
P(OMe)3 as external standard (δ = 139, relative to 85 % H3PO4, δ =
0.00). Elemental analyses were performed with a Vario EL analyzer from
Elementar Analysensysteme GmbH (Hanau, Germany). Melting points
were determined using sealed nitrogen purged capillaries on a Gallen-
kamp MFB 595 010 M melting point apparatus.
features expected for this type of molecules. Noteworthy is the
formation of 1D chains in the solid state of 1-I-3-Br-5-(FcC≡C)-
C6H3 and 1-(HC≡C)-3-(C≡C-bpy(Re(CO)3Cl))-5-(FcC≡C)-
C6H3, respectively, set up by strong π–π interactions between
aromatic rings of adjacent molecules.
Syntheses
Experimental Section
1-I-3-Br-5-(FcC≡C)-C6H3 (4): To a tetrahydrofuran solution (50 mL)
containing 1,3-Br2-5-(FcC≡C)-C6H3 (3) (1.0 g, 2.25 mmol) nBuLi
(1.41 mL, 2.25 mmol, 1.6 m in n-hexane) was slowly added at –80 °C.
The reaction solution was stirred for 1.5 hours at this temperature and
afterwards a solution of I2 (0.65 g, 2.56 mmol) dissolved in tetrahydro-
furan (20 mL) was added. After removal of the cooling bath, the solution
was stirred for 1 h at 25 °C and afterwards an aqueous sodium-thiosulfate
solution was added to destroy the excess of I2. The reaction mixture
was then extracted three times with dichloromethane (50 mL) and the
combined dichloromethane extracts were dried with MgSO4. Removal of
all volatiles in oil-pump vacuum gave a red solid. Yield: 0.99 g
(2.02 mmol, 90 % based on 3).
Materials and Methods
Trimethylsilylacetylene [16], 1,3-Br2-5-(FcC≡C)-C6H3 (3) [7, 17], ethy-
nylferrocene (2) [18], 5-ethynyl-2,2'-bipyridine (5) [19], [(Ph3P)AuCl]
(12) [14], [Re(CO)5Cl] (10) [20] and [{[Ti](μ-σ,π-C≡CSiMe3)2}-
Cu(N≡CMe)]PF6 (15) [12] were prepared following published proce-
dures. All other chemicals are commercially available and were used as
received.
All reactions were carried out under an atmosphere of purified nitrogen
using standard Schlenk techniques. n-Hexane and tetrahydrofuran were
purified by distillation from sodium/benzophenone ketyl; dichlorometh-
ane was purified by distillation from phosphorus pentoxide. Triethylam-
ine was dried by distillation from KOH. Infrared spectra were recorded Anal. calcd. for C18H12BrFeI (490.9) C 44.04, H 2.46: found C 44.83,
with a Perkin–Elmer FT-IR 1000 spectrometer. NMR spectra were re- H 2.72 %. IR (KBr): 2196 (s, νC≡CFc) cm–1. H NMR (δ, CDCl3): 4.25
1
1
corded with a Bruker Avance 250 spectrometer. H NMR spectra were (s, 5 H, C5H5), 4.28 (pt, JHH = 1.9 Hz, 2 H, C5H4), 4.50 (pt, JHH
recorded at 250.130 MHz (internal standard, relative to CDCl3, δ = 7.26) 1.9 Hz, 2 H, C5H4), 7.58 (pt, JHH = 1.6 Hz, 1 H, C6H3), 7.75 (pt, JHH
=
=
and 13C{1H} NMR spectra at 62.902 MHz (internal standard, relative to 1.6 Hz, 1 H, C6H3), 7.79 (pt, JHH = 1.6 Hz, 1 H, C6H3). 13C{1H} NMR
CDCl3, δ = 77.16). Chemical shifts are reported in δ units (parts per (δ, CDCl3): 64.1 (Ci/C5H4), 69.4 (CH/C5H4), 70.2 (C5H5), 71.8 (CH/
million) downfield from tetramethylsilane with the solvent as the refer- C5H4), 82.9 (C≡C), 91.9 (C≡C), 93.9 (Ci/C6H3), 122.7 (Ci/C6H3), 127.7
ence signal. 31P{1H}NMR spectra were recorded at 101.254 MHz with (Ci/C6H3), 133.4 (CH/C6H3), 138.6 (CH/C6H3), 138.8 (CH/C6H3).
2612
www.zaac.wiley-vch.de
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2010, 2607–2616

Transition-Metal Complexes with the 1,3,5-Triethynyl Benzene Linking Unit
3
3
1-Br-3-(bpy-C≡C)-5-(FcC≡C)-C6H3 (6) and 1,3-(bpy-C≡C)2-5- 7.62 (pt, JHH = 1.6 Hz, 1 H, C6H3), 7.83 (ddd, JH4'H3' = JH4'H5' = 7.6,
(FcC≡C)-C6H3 (7): 1-I-3-Br-5-(FcC≡C)-C6H3 (4) (500 mg, 1.02 mmol) 4JH4'H6' = 1.7 Hz, 1 H, H4'/bpy), 7.92 (dd, 3JH4H3 = 8.2, 4JH4H6 = 2.0 Hz,
and 5-ethynyl-2,2'-bipyridine (5) (185 mg, 1.03 mmol) were dissolved in 1 H, H4/bpy), 8.40–8.45 (m, 2 H, H3,H3'/bpy), 8.70 (ddd, 3JH6'H5' = 4.8,
5
4
diisopropylamine (40 mL). [(Ph3P)2PdCl2] (35 mg, 5 mol-%) and [CuI] 4JH6'H4' = 1.7, JH6'H3' = 1.0 Hz, 1 H, H6'/bpy), 8.80 (dd, JH6H4 = 2.0,
(18 mg, 10 mol-%) were added in a single portion. The thus obtained 5JH6H3 = 0.8 Hz, 1 H, H6/bpy). 13C{1H} NMR (δ, CDCl3): 64.6 (Ci/
reaction mixture was stirred for 3 hours at ambient temperature and after- C5H4), 69.2 (CH/C5H4), 70.2 (C5H5), 71.7 (CH/C5H4), 84.2 (C≡C), 87.4
wards at 40 °C for 12 hours. All volatile materials were evaporated in (C≡C), 90.3 (C≡C), 92.1 (C≡C), 96.0 (C≡C), 103.4 (C≡C), 120.0 (C5/
vacuo and the residue was purified by column chromatography (Silica bpy), 120.5 (C3/bpy), 121.5 (C3'/bpy), 123.3 (Ci/C6H3), 124.10 (Ci/
gel, diethyl ether-petroleum ether of ratio 1:1, v/v). The first fraction C6H3), 124.14 (C5'/bpy), 124.9 (Ci/C6H3), 133.9 (CH/C6H3), 134.2 (CH/
contained unreacted 4. The second orange fraction contained compound C6H3), 134.8 (CH/C6H3), 137.1 (C4'/bpy), 139.6 (C4/bpy), 149.5 (C6'/
6 and the third one organometallic 7. Yield: Complex 6: 430 mg bpy), 151.8 (C6/bpy), 155.3 (Ci/bpy), 155.6 (Ci/bpy).
(0.79 mmol, 78 % based on 4); complex 7: 45 mg (0.07 mmol, 7 %
1-(HC≡C)-3-(bpy-C≡C)-5-(FcC≡C)-C6H3 (9): A dichloromethane solu-
tion (25 mL) containing 1-(Me3SiC≡C)-3-(bpy-C≡C)-5-(FcC≡C)-C6H3
based on 4).
Compound 6: C30H19BrFeN2 (543.24) C 66.33, H 3.53, N 5.16; found C (8) (330 mg, 0.589 mmol) was cooled to 0 °C and [nBu4N]F (0.65 mL,
1
66.38, H 3.77, N 4.76 %. IR (KBr): 2211 (m, νC≡C) cm–1. H NMR (δ, 0.650 mmol, 1.0 m in tetrahydrofuran) was slowly added. After removal
CDCl3): 4.26 (s, 5 H, C5H5), 4.28 (pt, JHH = 1.9 Hz, 2 H, C5H4), 4.51 of the cooling bath, the reaction solution was stirred for 1 h and after-
3
3
(pt, JHH = 1.9 Hz, 2 H, C5H4), 7.32 (ddd, JH5'H4' = 7.8, JH5'H6' = 4.7, wards all volatile materials were removed in oil-pump vacuum. The ob-
4JH5'H3' = 1.0 Hz, 1 H, H5'/bpy), 7.60–7.64 (m, 3 H, C6H3), 7.83 (ddd, tained residue was purified on a Silica gel column (diethyl ether-petro-
4
3JH4'H3'
=
3JH4'H5' = 7.8, JH4'H6' = 1.7 Hz, 2 H, H4'/bpy), 7.93 (dd, leum ether mixture of ratio 3:2, v/v). After removal of the solvents, an
3JH4H3 = 8.2, 4JH4H6 = 2.2 Hz, 2 H, H4/bpy), 8.40–8.46 (m, 2 H, H3,H3'/ orange-red solid was obtained. Yield: 248 mg (0.508 mmol, 86 % based
bpy), 8.69 (ddd, 3JH6'H5' = 4.7, 4JH6'H4' = 1.7, 5JH6'H3' = 1.0 Hz, 2 H, H6'/
on 8).
bpy), 8.80 (dd, JH6H4 = 2.2, JH6H3 = 0.6 Hz, 2 H, H6/bpy). 13C{1H}
NMR (δ, CDCl3): 64.3 (Ci/C5H4), 69.3 (CH/C5H4), 70.2 (C5H5), 71.7
(CH/C5H4), 83.6 (C≡C), 88.1 (C≡C), 91.3 (C≡C), 91.4 (C≡C), 119.7 (C5/
bpy), 120.5 (C3/bpy), 121.5 (C3'/bpy), 122.1 (Ci/C6H3), 124.2 (C5'/bpy),
124.7 (Ci/C6H3), 126.3 (Ci/C6H3), 133.1 (CH/C6H3), 133.3 (CH/C6H3),
134.3 (CH/C6H3), 137.1 (C4'/bpy), 139.6 (C4/bpy), 149.5 (C6'/bpy),
151.8 (C6/bpy), 155.4 (Ci/bpy), 155.5 (Ci/bpy).
4
5
Anal. calcd. for C32H20FeN2 (488.37) C 78.70, H 4.13, N 5.74; found C
78.49, H 4.41, N 5.62 %. IR (KBr): 3290 (m, ν≡C–H), 2212 (m, νC≡C),
1
2100 (w, νC≡CH) cm–1. H NMR (δ, CDCl3): 3.14 (s, 1 H, ≡CH), 4.26
(s, 5 H, C5H5), 4.27 (pt, JHH = 1.9 Hz, 2 H, C5H4), 4.51 (pt, JHH
=
=
3
3
4
1.9 Hz, 2 H, C5H4), 7.33 (ddd, JH5'H4' = 7.8, JH5'H6' = 4.7, JH5'H3'
1.0 Hz, 1 H, H5'/bpy), 7.59 (pt, JHH = 1.6 Hz, 1 H, C6H3), 7.61 (pt,
J
HH = 1.6 Hz, 1 H, C6H3), 7.66 (pt, JHH = 1.6 Hz, 1 H, C6H3), 7.84 (ddd,
4
Compound 7: C42H26FeN4 (642.54) C 78.51, H 4.08, N 8.72; found C
3JH4'H3'
=
3JH4'H5' = 7.8, JH4'H6' = 1.7 Hz, 1 H, H4'/bpy), 7.94 (dd,
78.56, H 4.22, N 8.51 %. IR (KBr): 2214 (m, νC≡C) cm–1. H NMR (δ, 3JH4H3 = 8.2, 4JH4H6 = 2.2 Hz, 1 H, H4/bpy), 8.40–8.46 (m, 2 H, H3,H3'/
CDCl3): 4.27 (s, 5 H, C5H5), 4.28 (pt, JHH = 1.9 Hz, 2 H, C5H4), 4.53 bpy), 8.70 (ddd, 3JH6'H5' = 4.7, 4JH6'H4' = 1.7, 5JH6'H3' = 1.0 Hz, 1 H, H6'/
1
(pt, JHH = 1.9 Hz, 2 H, C5H4), 7.33 (ddd, JH5'H4' = 7.9, JH5'H6' = 4.7, bpy), 8.81 (dd, JH6H4 = 2.2, JH6H3 = 0.8 Hz, 1 H, H6/bpy). 13C{1H}
3
3
4
5
4JH5'H3' = 1.0 Hz, 1 H, H5'/bpy), 7.67–7.71 (m, 3 H, C6H3), 7.83 (ddd, NMR (δ, CDCl3): 64.5 (Ci/C5H4), 69.3 (CH/C5H4), 70.2 (C5H5), 71.7
4
3JH4'H3'
=
3JH44'H5' = 7.9, JH4'H6' = 1.7 Hz, 1 H, H4'/bpy), 7.94 (dd, (CH/C5H4), 78.7 (C≡C), 82.2 (C≡C), 84.1 (C≡C), 87.7 (C≡C), 90.6
3JH4H3 = 8.2, JH4H6 = 2.0 Hz, 2 H, H4/bpy), 8.43 (ddd, JH3'H4' = 7.9, (C≡C), 92.0 (C≡C), 119.9 (C5/bpy), 120.5 (C3/bpy), 121.6 (C3'/bpy),
3
4JH3'H5' = 5JH3'H6' = 1.0 Hz, 2 H, H3'/bpy), 8.44 (dd, 3JH3H4 = 8.2, 5JH3H6
=
=
123.1 (Ci/C6H3), 123.5 (Ci/C6H3), 124.2 (C5'/bpy), 125.1 (Ci/C6H3),
134.0 (CH/C6H3), 134.6 (CH/C6H3), 134.9 (CH/C6H3), 137.1 (C4'/bpy),
3
4
5
0.8 Hz, 2 H, H3/bpy), 8.70 (ddd, JH6'H5' = 4.7, JH6'H4' = 1.7, JH6'H3'
1.0 Hz, 2 H, H6'/bpy), 8.83 (dd, 4JH6H4 = 2.2, 5JH6H3 = 0.8 Hz, 2 H, H6/ 139.6 (C4/bpy), 149.5 (C6'/bpy), 151.9 (C6/bpy), 155.3 (Ci/bpy), 155.5
bpy). 13C{1H} NMR (δ, CDCl3): 64.5 (Ci/C5H4), 69.3 (CH/C5H4), 70.2 (Ci/bpy).
(C5H5), 71.7 (CH/C5H4), 84.1 (C≡C), 87.7 (C≡C), 90.6 (C≡C), 92.0
1-(HC≡C)-3-(C≡C-bpy(Re(CO)3Cl))-5-(FcC≡C)-C6H3
(11):
(C≡C), 119.9 (C5/bpy), 120.5 (C3/bpy), 121.5 (C3'/bpy), 123.6 (Ci/
C6H3), 124.2 (C5'/bpy), 125.2 (Ci/C6H3), 133.6 (CH/C6H3), 134.5 (CH/
C6H3), 137.1 (C4'/bpy), 139.6 (C4/bpy), 149.5 (C6'/bpy), 151.9 (C6/bpy),
155.3 (Ci/bpy), 155.5 (Ci/bpy).
[Re(CO)5Cl] (10) (150 mg, 0.415 mmol) was dissolved in toluene
(70 mL) at 60 °C. To this solution 1-(HC≡C)-3-(bpy-C≡C)-5-(FcC≡C)-
C6H3 (9) (230 mg, 0.471 mmol) was added in a single portion and stir-
ring was continued for 8 hours at 60 °C whereby the formed product
1-(Me3SiC≡C)-3-(bpy-C≡C)-5-(FcC≡C)-C6H3 (8): To 1-Br-3-(bpy- partly precipitated. After cooling to ambient temperature, the toluene was
C≡C)-5-(FcC≡C)-C6H3 (6) (400 mg, 0.74 mmol) dissolved in diisopro- removed in vacuo and the obtained residue was dissolved in dichloro-
pylamine (30 mL) were added trimethylsilylacetylene (350 mg, methane (5 mL). Addition of n-hexane (30 mL) resulted in the precipita-
3.57 mmol), [(Ph3P)2Cl2Pd] (25 mg, 5 mol-%) and [CuI] (13 mg, 10 tion of the title compound. After washing the precipitate three times with
mol-%). After stirring this reaction mixture for 20 hours at 50 °C all diethyl ether-n-hexane mixtures (ratio 1:1, v/v) and drying the orange
volatiles were evaporated in oil-pump vacuum and the residue was chro- solid in oil-pump vacuum, 245 mg (0.309 mmol, 74 % based on 9) of
matographed on Silica gel using a mixture of diethyl ether-petroleum 11 could be isolated.
ether (1:1, v/v) as eluent. After removal of the solvents, complex 8 was
Anal. calcd. for C35H20ClFeN2O3Re (794.06) C 52.94, H 2.54, N 3.53;
obtained as an orange solid material. Yield: 355 mg (0.63 mmol, 86 %
found C 53.33, H 2.40, N 3.39 %. IR (KBr): 3294 (m, ν≡C–H), 2211 (m,
based on 6).
1
νC≡C), 2022, 1914, 1894 (s, νCO) cm–1. H NMR (δ, CDCl3): 4.26 (s, 5
Anal. calcd. for C35H28FeN2Si (560.55) C 74.99, H 5.03, N 5.00; found H, C5H5), 4.28 (pt, JHH = 1.9 Hz, 2 H, C5H4), 4.53 (pt, JHH = 1.9 Hz, 2
C 74.57, H 5.35, N 4.91 %. IR (KBr): 2214 (m, νC≡C), 2157 (m, νC≡CSi
)
H, C5H4), 7.55 (ddd, 3JH5'H4' = 7.6, 3JH5'H6' = 4.6, 4JH5'H3' = 1.0 Hz, 1 H,
1
cm–1. H NMR (δ, CDCl3): 0.26 (s, 9 H, SiMe3), 4.25 (s, 5 H, C5H5), H5'/bpy), 7.62 (pt, JHH = 1.6 Hz, 1 H, C6H3), 7.65 (pt, JHH = 1.6 Hz, 1
4.27 (pt, JHH = 1.9 Hz, 2 H, C5H4), 4.50 (pt, JHH = 1.9 Hz, 2 H, C5H4), H, C6H3), 7.68 (pt, JHH = 1.6 Hz, 1 H, C6H3), 8.01–8.10 (m, 2 H, H4,H4'/
3
3
4
7.32 (ddd, JH5'H4' = 7.6, JH5'H6' = 4.8, JH5'H3' = 1.0 Hz, 1 H, H5'/bpy), bpy), 8.14–8.20 (m, 2 H, H3,H3'/bpy), 9.07 (ddd, 3JH6'H5' = 4.6, 4JH6'H4'
=
=
5
4
5
7.58 (pt, JHH = 1.6 Hz, 1 H, C6H3), 7.60 (pt, JHH = 1.6 Hz, 1 H, C6H3), 1.7, JH6'H3' = 1.0 Hz, 1 H, H6'/bpy), 9.15 (dd, JH6H4 = 2.2, JH6H3
Z. Anorg. Allg. Chem. 2010, 2607–2616
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
2613

R. Packheiser, T. Rüffer, P. Ecorchard, H. Lang
[{[Ti](μ-σ,π-C≡CSiMe3)2}Cu(N≡CMe)]PF6 (15) (50 mg,
ARTICLE
0.8 Hz, 1 H, H6/bpy). 13C{1H} NMR (δ, CDCl3): 64.3 (Ci/C5H4), 69.4 ing
(CH/C5H4), 70.2 (C5H5), 71.8 (CH/C5H4), 79.1 (C≡C), 81.8 (C≡C), 83.8 0.064 mmol), 1-((Ph3P)AuC≡C)-3-(C≡C-bpy)-5-(FcC≡C)-C6H3 (14)
(C≡C), 84.5 (C≡C), 91.2 (C≡C), 96.2 (C≡C), 122.0 (C5/bpy), 122.9 (C3/ (60 mg, 0.063 mmol) was added in a single portion. During the course
bpy), 123.4 (Ci/C6H3), 123.7 (C3'/bpy), 124.0 (Ci/C6H3), 125.4 (Ci/ of the reaction (3 hours, 25 °C) the color of the reaction solution changed
C6H3), 127.3 (C5'/bpy), 134.1 (CH/C6H3), 134.7 (CH/C6H3), 135.9 (CH/ from orange to red. After removal of all volatile materials in oil-pump
C6H3), 139.1 (C4'/bpy), 141.0 (C4/bpy), 153.4 (C6'/bpy), 154.2 (Ci/bpy), vacuum the residue was dissolved in dichloromethane (3 mL) and the
155.19 (Ci/bpy), 155.24 (C6/bpy), 189.2 (CO), 197.0 (CO).
title complex was precipitated by addition of n-hexane (20 mL). The
obtained precipitate was washed twice with diethyl ether (2 × 10 mL).
Drying the solid material in oil-pump vacuum gave 92 mg (0.055 mmol,
87 % based on 15) of 16.
1-((Ph3P)AuC≡C)-3-(C≡C-bpy(Re(CO)3Cl))-5-(FcC≡C)-C6H3 (13):
To a tetrahydrofuran (5 mL) and diethylamine (15 mL) solution of 1-
(HC≡C)-3-(C≡C-bpy(Re(CO)3Cl))-5-(FcC≡C)-C6H3
(11)
(80 mg,
0.101 mmol) and [(Ph3P)AuCl] (12) (50 mg, 0.101 mmol) [CuI] (1 mg)
was added. After stirring this reaction solution for 15 hours at 25 °C all
volatile materials were evaporated in oil-pump vacuum and the residue
was purified by column chromatography (Silica gel, toluene-tetrahydro-
furan mixture of ratio 3:1, v/v). The title complex could be eluted as an
orange band. After removal of all volatiles in oil-pump vacuum an orange
solid remained. Yield: 35 mg (0.033 mmol, 33 % based on 11).
Anal. calcd. for C76H78AuCuF6FeN2P2Si4Ti·¼CH2Cl2 (1693.18) C 54.09,
H 4.67, N 1.65; found C 54.00, H 4.89, N 1.62 %. IR (KBr): 2211 (m,
ν
C≡C), 2115 (w, νC≡CAu), 1924 (m, νC≡CTi) cm–1. 1H NMR (δ, CDCl3): –
0.48 (s, 18 H, SiMe3), 0.28 (s, 9 H, SiMe3), 0.30 (s, 9 H, SiMe3), 4.23
(s, 5 H, C5H5), 4.25 (pt, JHH = 1.9 Hz, 2 H, C5H4), 4.49 (pt, JHH
=
1.9 Hz, 2 H, C5H4), 5.30 (s, ¼ × 2 H, CH2Cl2), 6.27–6.32 (m, 8 H,
C5H4Si), 7.41–7.57 (m, 15 H, C6H5), 7.59 (pt, JHH = 1.6 Hz, 1 H, C6H3),
7.63 (pt, JHH = 1.6 Hz, 1 H, C6H3), 7.65 (pt, JHH = 1.6 Hz, 1 H, C6H3),
7.69–7.75 (m, 1 H, H5'/bpy), 8.21–8.30 (m, 2 H, H4,H4'/bpy), 8.51–
8.69 (m, 4 H, H3,H3',H6,H6'/bpy). 31P{1H} NMR (δ, CDCl3): –145.1
(septublet, 1JPF = 713 Hz, PF6), 41.1 (s, AuPPh2). ESI MS (m/z): 1525.3
([M – PF6]+).
Anal. calcd. for C53H34AuClFeN2O3PRe·1/4C7H8 (1275.33) C 51.56, H
2.85, N 2.20; found C 51.71, H 2.89, N 2.78 %. IR (KBr): 2212 (m,
1
ν
C≡C), 2115 (w, νC≡CAu), 2021, 1915, 1896 (s, νCO) cm–1. H NMR (δ,
CDCl3): 2.36 (s, ¼ × 3 H, CH3, toluene), 4.25 (s, 5 H, C5H5), 4.27 (pt,
JHH = 1.9 Hz, 2 H, C5H4), 4.52 (pt, JHH = 1.9 Hz, 2 H, C5H4), 7.17 (m,
¼ × 3 H, toluene), 7.25 (m, ¼ × 2 H, toluene), 7.43–7.61 (m, 15 H
(C6H5) + 1 H (C6H3) + 1 H (H5'/bpy)), 7.63 (pt, JHH = 1.6 Hz, 1 H,
C6H3), 7.67 (pt, JHH = 1.6 Hz, 1 H, C6H3), 8.02–8.20 (m, 4 H,
1,3-(C≡C-bpy(Ru(tBu2bpy)2)2-5-(FcC≡C)-C6H3
(18):
To
[(tBu2bpy)2Cl2Ru] (17) (60 mg, 0.085 mmol) dissolved in ethanol
(25 mL) 1,3-(bpy-C≡C)2-5-(FcC≡C)-C6H3 (7) (25 mg, 0.039 mmol) was
added in a single portion and the reaction solution was heated for 20
hours to reflux whereby a color change from purple to red occurred.
After cooling to ambient temperature, an aqueous solution (5 mL) of
[H4N]PF6 (50 mg, 0.307 mmol) was added and the solid precipitated was
separated and washed with water, ethanol, and diethyl ether, and was
than dried in oil-pump vacuum. The title complex was obtained as a red
solid. Yield: 64 mg (0.026 mmol, 66 % based on 7).
3
4
5
H3,H3',H4,H4'/bpy), 9.07 (ddd, JH6'H5' = 4.6, JH6'H4' = 1.7, JH6'H3'
=
1.0 Hz, 1 H, H6'/bpy), 9.14 (dd, 4JH6H4 = 2.2, 5JH6H3 = 0.8 Hz, 1 H, H6/
bpy). 31P{1H} NMR (δ, CDCl3): 41.1 (s, AuPPh2). ESI-MS (m/z):
1253.4 ([M + H]+).
1-((Ph3P)AuC≡C)-3-(C≡C-bpy)-5-(FcC≡C)-C6H3 (14): [(Ph3P)AuCl]
(12) (130 mg, 0.263 mmol) and 1-(HC≡C)-3-(bpy-C≡C)-5-(FcC≡C)-
C6H3 (9) (135 mg, 0.276 mmol) were dissolved in tetrahydrofuran
(10 mL). Diethylamine (15 mL) and [CuI] (1 mg) were added at ambient
temperature. After 8 hours of stirring at this temperature, all volatiles
were evaporated in oil-pump vacuum. Column chromatography of the
residue (Silica gel, diethyl ether-dichloromethane mixture of ratio 10:1,
v/v) gave an orange band from which 14 could be isolated as an orange
solid. Yield: 165 mg (0.174 mmol, 66 % based on 9).
Anal. calcd. for C114H122FeF24N12P4Ru2 (2499.14) C 54.79, H 4.96, N
6.72; found C 55.11, H 4.96, N 6.42 %. IR (KBr): 2211 (m, νC≡C) cm–1.
1H NMR (δ, d6-Aceton): 1.39 (s, 18 H, tBu), 1.40 (s, 18 H, tBu), 1.44
(s, 9 H, tBu), 4.26 (s, 5 H, C5H5), 4.38 (pt, JHH = 1.9 Hz, 2 H, C5H4),
4.53 (pt, JHH = 1.9 Hz, 2 H, C5H4), 7.48–7.64 (m, bpy/tBu2bpy), 7.82–
8.06 (m, bpy/tBu2bpy), 8.21–8.35 (m, bpy/tBu2bpy), 8.80–8.93 (m, bpy/
Anal. calcd. for C50H34AuFeN2P (946.62) C 63.44, H 3.62, N 2.96; found
1
tBu2bpy). 31P{1H} NMR (δ,d6-Aceton): –145.1 (septet, JPF = 713 Hz,
C 63.33, H 3.77, N 2.87 %. IR (KBr): 2211 (m, νC≡C), 2116 (w, νC≡CAu
)
PF6). ESI MS (m/z): 479.2 ([M – 4 PF6]4+), 639.6 ([M – 4 PF6
Ru(tBu2bpy)2]2+).
–
cm–1. 1H NMR (δ, CDCl3): 4.24 (s, 5 H, C5H5), 4.25 (pt, JHH = 1.9 Hz,
2 H, C5H4), 4.50 (pt, JHH = 1.9 Hz, 2 H, C5H4), 7.31 (ddd, 3JH5'H4' = 7.6,
3JH5'H6' = 4.9, 4JH5'H3' = 1.0 Hz, 1 H, H5'/bpy), 7.39–7.64 (m, 15 H (C6H5)
+ 3 H (C6H3)), 7.82 (ddd, 3JH4'H3' = 3JH4'H5' = 7.6, 4JH4'H6' = 1.7 Hz, 1 H,
3
4
X-ray Structure Determination
H4'/bpy), 7.92 (dd, JH4H3 = 8.2, JH4H6 = 2.2 Hz, 1 H, H4/bpy), 8.41
3
5
3
(dd, JH3H4 = 8.2, JH3H6 = 0.8 Hz, 1 H, H3/bpy), 8.42 (ddd, JH3'H4'
=
The X-ray structure measurements for 4 and 11 were performed with an
Oxford Gemini S diffractomter. The structures were solved by direct
methods using SHELXS-97 [21] and refined by full-matrix least-square
procedures on F2 using SHELXL-97 [22]. All non-hydrogen atoms were
refined anisotropically. All hydrogen atom positions were refined using
a riding model. In case of 11 the CH2Cl2 molecule as noncoordinating
packing solvent has been refined disordered on two positions, with occu-
pation factors of 0.49 (C36, Cl1, Cl2) and 0.51 (C36', Cl1', Cl2').
4
5
3
7.6, JH3'H5' = JH3'H6' = 1.0 Hz, 1 H, H3'/bpy), 8.69 (ddd, JH6'H5' = 4.9,
4JH6'H4' = 1.7, JH6'H3' = 1.0 Hz, 1 H, H6'/bpy), 8.80 (dd, JH6H4 = 2.2,
5JH6H3 = 0.8 Hz, 1 H, H6/bpy). 13C{1H} NMR (δ, CDCl3): 65.0 (Ci/
C5H4), 69.0 (CH/C5H4), 70.2 (C5H5), 71.6 (CH/C5H4), 84.7 (C≡C), 86.8
(C≡C), 89.4 (C≡C), 92.8 (C≡C), 102.4 (d, JCP = 27 Hz, AuC≡C), 120.3
(C5/bpy), 120.4 (C3/bpy), 121.5 (C3'/bpy), 122.9 (Ci/C6H3), 124.0 (C5'/
5
4
bpy), 124.5 (Ci/C6H3), 125.8 (AuC≡C), 125.9 (Ci/C6H3), 129.3 (d, 3JCP
11.4 Hz, Cm/C6H5), 129.8 (d, 1JCP = 56.1 Hz, Ci/C6H5), 131.8 (d, 4JCP
=
=
2.4 Hz, Cp/C6H5), 132.7 (CH/C6H3), 134.4 (d, 1JCP = 13.8 Hz, Co/C6H5),
134.5 (CH/C6H3), 135.6 (CH/C6H3), 137.1 (C4'/bpy), 139.5 (C4/bpy),
149.4 (C6'/bpy), 151.9 (C6/bpy), 155.0 (Ci/bpy), 155.6 (Ci/bpy). 31P{1H}
NMR (δ, CDCl3): 41.2 (s, AuPPh2).
The crystallographic data for 4 and 11 have been deposited with the
Cambridge Crystallographic Data Centre as supplementary publication
no. CCDC-753340 (4) and CCDC-753341 (11). Copies of this informa-
tion can be obtained free of charge on application to CCDC, 12 Union
Road, Cambridge CB2 1ET, UK. [Fax: +44-1223-336033, E-Mail:
[1-((Ph3P)AuC≡C)-3-(C≡C-bpy({[Ti](μ-σ,π-C≡CSiMe3)2}Cu))-5-
(FcC≡C)-C6H3]PF6 (16): To a tetrahydrofuran solution (25 mL) contain- deposit@ ccdc.cam.ac.uk].
2614
www.zaac.wiley-vch.de
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2010, 2607–2616

Transition-Metal Complexes with the 1,3,5-Triethynyl Benzene Linking Unit
G. I. Jenkins, P. A. Schauer, B. Szczepaniak, B. W. Skelton, C. Tan,
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Acknowledgement
Financial support from the Deutsche Forschungsgemeinschaft and the
Fonds der Chemischen Industrie is gratefully acknowledged.
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