Mixed transition-metal complexes based on multitopic 1,3,5-triethynyl- and 1-diphenylphosphino-3,5-diethynyl-benzene linking units

Article abstract of DOI:10.1016/j.ica.2010.10.029

The synthesis and reaction chemistry of heteromultimetallic transition metal complexes in which Fc, [(η⁶-C₆H ₅)Cr(CO)₃], [(Ar₃P)Au], [AuCC-bpy] and [{[Ti](μ-σ,π-CCSiMe₃)₂}Cu]⁺ units (Fc = (η⁵-C₅H₄)(η⁵-C ₅H₅)Fe; [Ti] = (η⁵-C₅H ₄SiMe₃)₂Ti; bpy = 2,2′-bipyridyl-5-yl) are linked by alkynyl-, benzene- and phosphane- or bipyridyl-based connecting moieties is discussed. In context with this background the preparation of neutral heterotrimetallic 1-(FcCC)-3-[(CO)₃Cr(η⁶- C₆H₅CC)]-5-[(Ph₃P)AuCC]C₆H ₃ (10) and ionic heteropentametallic [1-(FcCC)-3-[(CO) ₃Cr(η⁶-C₆H₅CC)]-5-[(PPh ₂)AuCC-bpy({[Ti](μ-σ,π-CCSiMe₃) ₂}Cu)]C₆H₃](PF₆) (19) from 1-iodo-3,5-dibromobenzene (1) is reported by applying consecutive reaction methodologies including substitution, complexation and carbon-carbon cross-coupling reactions. The identities of all complexes have been confirmed by elemental analysis and IR, ¹H and ³¹P{¹H} NMR spectroscopy; heteropentametallic 19 was additionally characterized by ESI-TOF mass-spectrometry.

Full text of DOI:10.1016/j.ica.2010.10.029

Inorganica Chimica Acta 366 (2011) 177–183
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Inorganica Chimica Acta
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Mixed transition–metal complexes based on multitopic 1,3,5-triethynyl-
and 1-diphenylphosphino-3,5-diethynyl-benzene linking units
⇑
Rico Packheiser, Heinrich Lang
Technische Universität Chemnitz, Fakultät für Naturwissenschaften, Institut für Chemie, Lehrstuhl für Anorganische Chemie, Straße der Nationen 62, 09111 Chemnitz, Germany
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 16 June 2010
Received in revised form 19 October 2010
Accepted 26 October 2010
Available online 13 November 2010
The synthesis and reaction chemistry of heteromultimetallic transition metal complexes in which Fc,
[(
C5H4)(
and phosphane- or bipyridyl-based connecting moieties is discussed. In context with this background
the preparation of neutral heterotrimetallic 1-(FcC„C)-3-[(CO)3Cr(
6-C6H5C„C)]-5-[(Ph3P)AuC„C]C6H3
(10) and ionic heteropentametallic [1-(FcC„C)-3-[(CO)3Cr(
6-C6H5C„C)]-5-[(PPh2)AuC„C-bpy({[Ti](
-C„CSiMe3)2}Cu)]C6H3](PF6) (19) from 1-iodo-3,5-dibromobenzene (1) is reported by applying con-
g l-r,p -
6-C6H5)Cr(CO)3], [(Ar3P)Au], [AuC„C-bpy] and [{[Ti]( -C„CSiMe3)2}Cu]+ units (Fc = (g5
g
5-C5H5)Fe; [Ti] = (g5-C5H4SiMe3)2Ti; bpy = 2,20-bipyridyl-5-yl) are linked by alkynyl-, benzene-
g
g
l-
Keywords:
r,p
Heteromultimetallic
Gold(I) acetylide
Ferrocene
Chromiumcarbonyl
Organometallic p-tweezer
secutive reaction methodologies including substitution, complexation and carbon–carbon cross-coupling
reactions.
The identities of all complexes have been confirmed by elemental analysis and IR, 1H and 31P{1H} NMR
spectroscopy; heteropentametallic 19 was additionally characterized by ESI-TOF mass-spectrometry.
Ó 2010 Elsevier B.V. All rights reserved.
1. Introduction
atoms with the 1,3,5-triethynyl benzene and the 1,3-diethynyl-5-
diphenylphosphino benzene core as linking unit.
To connect different early and/or late transition–metal complex
fragments in one molecule by forming (hetero)multimetallic orga-
nometallic complex systems is from the viewpoint of synthetic
chemistry a challenge because multitopic and reactive coordination
sites at the central bridging unit are required. So far mainly alkynyls
[1,2] or alkynyl-, allenylidene- and/or carbene-based organic mole-
cules including 1,4-diethynyl benzene [3,4], 1,3,5-triethynyl
benzene [5,6], 1-ethynyl-4-diphenylphosphino benzene [7], as well
as alkynyl-functionalized (poly)pyridyls [8,9] or thiophenes [10,11]
were used as connecting units. Recently, we extended this family of
bridging entities by introducing the 1,3-diethynyl-5-diphenylphos-
phino benzenemolecule[12]. This compoundcanserve as a versatile
building block allowing the preparation of carbon-rich complexes of
higher nuclearity in three directions,i.e., heterotetra- to heterohexa-
metallic complexes [12]. Electronic-based communication between
individual transition metal sub-units along the 1,3,(5)-substituted
2. Results and discussion
2.1. Synthesis
In order to prepare heterotrimetallic 1-(FcC„C)-3-[(CO)3Cr(g6
-
C6H5C„C)]-5-[(Ph3P)AuC„C]C6H3 (10) we followed the reaction
methodologies shown in Scheme 1. A modified synthesis procedure
for the preparation of 1-(FcC„C)-3,5-Br2-C6H3 (3) [5a,6e] was used,
whereby 1-iodo-3,5-dibromobenzene (1) was reacted with ethynyl-
ferrocene (2) at 40 °C following the Sonogashira carbon–carbon
cross-coupling protocol [6e,14]. The more reactive aryl–iodo bond
allowed the selective introduction of one organometallic FcC„C
moiety. Thus formed 3, further reacted with [(CO)3Cr(g6
-
C6H5C„CH)] (4) in HNiPr2 as solvent containing catalytic amounts
of [(Ph3P)2PdCl2] and [CuI] to produce heterobimetallic
1-(FcC„C)-3-[(CO)3Cr(g
6-C6H5C„C)]-5-Br-C6H3 (5). For comple-
benzene
p-backbone was studied as well. It was found that the
tion of the reaction, heating of the reaction mixture to 80 °C was nec-
essary. The reaction of 3 with 4 always produced as side product (ca.
appropriate conjugated organic spacers mediate significant elec-
tronic interactions between the corresponding transition metal cen-
ters as evidenced by electrochemical studies [5,6c,13].
5%) the disubstituted molecule 1-(FeC„C)-3,5-[(CO)3Cr(g6
-
C6H5C„C)]2C6H3. This organometallic compound could be sepa-
rated from 5 by column chromatography (Section 4). Compound 5
gave withan excess of trimethylsilylacetylene (6) the trialkynylben-
We here describe a new series of heteromultimetallic com-
plexes featuring titanium, chromium, iron, copper and gold metal
zene species 1-(FcC„C)-3-[(CO)3Cr(
C6H3 (7), which by desilylation with [nBu4N]F afforded 1-(FcC„C)-
3-[(CO)3Cr(
6-C6H5C„C)]-5-(HC„C)C6H3 (8) as a yellow solid in
excellent yield (Scheme 1).
g
6-C6H5C„C)]-5-(Me3SiC„C)
⇑
g
Corresponding author. Tel.: +49 371 531 21210; fax: +49 371 531 21219.
E-mail address: heinrich.lang@chemie.tu-chemnitz.de (H. Lang).
0020-1693/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2010.10.029

178
R. Packheiser, H. Lang / Inorganica Chimica Acta 366 (2011) 177–183
Scheme 1. Consecutive synthesis of heterotrimetallic 10.
The last step in the synthesis of 10 included the dehydrohalogen-
metallic p-tweezer [{[Ti](l-r,p-C„CSiMe3)2}Cu(N„CMe)](PF6)
ation reaction of 8 with [(Ph3P)AuCl] (9) in a 1:1 mixture of tetrahy-
drofuran–diethylamine at ambient temperature. It was necessary to
add a catalytic amount of [CuI] to the tetrahydrofuran–diethylamine
reaction medium for completion of the reaction [15]. After appropri-
ate work-up, heterotrimetallic 10 could be isolated as a yellow-
orange solid in a yield of 38%.
(18) to obtain a molecule of higher nuclearity (Scheme 2). Exchange
of the weakly bonded acetonitrile ligand in 18 by the better
donor–acceptor 2,20-bipyridine gave heteropentametallic
[1-(FcC„C)-3-[(CO)3Cr(
-C„CSiMe3)2}Cu)]C6H3](PF6) (19) which, after appropriate
g
6-C6H5C„C)]-5-[(PPh2)AuC„C-bpy({[Ti]-
(l-r,p
work-up, was obtained in good yield (Section 4). In this molecule five
different metal atoms including titanium, chromium, iron, copper
and gold are connected via carbon-rich organic bridging units such
as alkynyls, a 1,3,5-substituted benzene entity and a bipyridyl
moiety.
For the overall synthesis of complex [1-(FcC„C)-3-[(CO)3Cr(g6
C6H5C„C)]-5-[(PPh2)AuC„C-bpy({[Ti]( -C„CSiMe3)2}Cu)]C6
-
l-r,p
H3](PF6) (19) featuring five different transition metal atoms we also
chose 1-(FcC„C)-3,5-Br2-C6H3 (3) as key starting material [5a,6b].
Halide exchange and Sonogashira carbon–carbon cross-coupling
reactions play an essential role in the synthesis of 1-(FcC„C)-3-
It appeared that all compounds with the [(CO)3Cr(g6
-
C6H5C„C)] fragment are highly reactive both in solution as well
as in the solid state. Even under inert gas atmosphere they rapidly
decompose to products which could not be further characterized,
due to their insolubility in common organic solvents. The process
of decomposition is even more facilitated, when these molecules
were exposed to air. In addition, these compounds are sensitive
to light and therefore should be handled and stored in the dark.
Out of these reasons the appropriate molecules are restricted to
certain characterization methods (see below). This was disappoint-
ing to us because one of our goals was to carry out spectro-electro-
chemical studies to show if between the appropriate transition
metal centers electron transfer is observed as recently demon-
strated by similar molecules [6c,13].
[(CO)3Cr(g
6-C6H5C„C)]-5-PPh2-C6H3 (13) (Scheme 2). Selective
lithiation of one bromo substituent in 3 gave [Li-3] which further
reacted with chlorodiphenylphosphine (11) to afford orange-red
1-(FcC„C)-3-Br-5-PPh2-C6H3 (12) byconcomitant formationof lith-
ium chloride. Treatment of the latter molecule with equimolar
amounts of [(CO)3Cr(g
6-C6H5C„CH)] (4) in presence of
[(Ph3P)2PdCl2]/[CuI] produced 13. However, this molecule could
only be isolated in 23% yield (Section 4). To improve the amount of
13 by changing the reaction conditions, either using higher temper-
ature or choosing other amines, was not successful, i.e., at higher
temperatures this molecule rapidly decomposed to yield solid mate-
rials which are not anymore soluble in common organic solvents
(vide supra). Just as little, complex 13 represents a very reactive com-
pound which strictly must be handled under inert gas atmosphere.
A possibility to introduce a transition metal fragment with a fur-
ther coordination site allowing to incorporate other metal building
blocks is given by the successive reaction of the tertiary phosphine
13 with [(tht)AuCl] (14) (tht = tetrahydrothiophene) and 5-ethy-
nyl-2,20-bipyridine (16), respectively. Thus, 13 was reacted with 14
in tetrahydrofuran as solvent at ambient temperature, whereby 15
could be isolated as an orange solid. Reacting heterotrimetallic 15
with 5-ethynyl-2,20-bipyridine (16) in a diethylamine–tetrahydro-
furan mixture gave after column chromatography the desired
gold(I)–alkynyl complex 17 in reasonable yield (Scheme 2, Section
4). Due to the presence of a pendant 2,20-bipyridyl fragment, com-
plex 17 was exemplarily reacted with the heterobimetallic organo-
2.2. Characterization
The identities of 3, 5, 7, 8, 10, 12, 13, 15, 17 and 19 have been
confirmed by elemental analysis, IR and 1H, 13C{1H} and 31P{1H}
NMR spectroscopy as well as ESI-TOF mass-spectrometry (19).
The IR spectra of all compounds are characterized by a mC
„
CFc
vibration at ca. 2210 cmꢀ1. For the AuC„C unit a characteristic
C„C frequency is observed at 2116 (17) and 2118 cmꢀ1 (10, 19),
respectively [16]. Noteworthy is that the predictable weak mC
„
C
absorptions for the [(CO)3Cr(
g
6-C6H5C„C)] (3, 5, 7, 8, 10, 13, 15,
17 and 19) and the titanium acetylide units (19) are covered
by the two very intense carbonyl absorptions at ca. 1970
and 1895 cmꢀ1 typical for the (CO)3Cr building block with C3v

R. Packheiser, H. Lang / Inorganica Chimica Acta 366 (2011) 177–183
179
Scheme 2. Reaction sequence for the synthesis of heteropentametallic 19.
symmetry (Section 4) [17]. The progress of the reaction of 7 with
[nBu4N]F to give 8 could be monitored by IR spectroscopy, since
the C„C vibration for the Me3SiC„C unit in 7 at 2156 cmꢀ1 grad-
ually disappears during the course of the reaction and a new band
ways appear as a singlet (C5H5 annulene) and two pseudo-triplets
(C5H4 moiety, JHH = 1.9 Hz) in the range of 4.2–4.6 ppm. Upon coor-
dination of the 2,20-bipyridyl moiety to copper(I) as given in 19, the
separated and well-resolved signals of this entity evince up- and
downfield shifts forming broad multiplets. Most expressive for
the formation of 19 is the highfield shift of the Me3SiC„C protons
of the bis(alkynyl)titanocene upon coordination of the bipyridyl
at 3306 cmꢀ1 appears which can be assigned to the mC
„
fre-
CH
quency. The mC
„
absorption is, however, covered by the CO
C
absorptions (vide supra).
The 31P{1H} NMR spectra of 12, 13, 15, 17 and 19 indicate the
presence of a single phosphorus environment (Section 4). The
chemical shift of the benzene-bonded PPh2 group is almost inde-
pendent of the appropriate substitution pattern of the benzene
core (12, ꢀ5.6; 13, ꢀ6.2 ppm) which is typical for such type of con-
nectivities [7,12]. Upon coordination of the diphenylphosphino
group to the AuCl fragment a representative shift to lower field
(15, 32.5 ppm) is observed. The exchange of Cl (15) by C„C-bpy
(17) induced a further shift to 40.8 ppm. In heteropentametallic
19 next to the resonance signal of the Ph2PAu unit at 41.2 ppm,
indicating that there is almost no influence on the chemical shift
of the Ph2P group by changing from 17 to 19, a second resonance
unit to the organometallic p-tweezer-stabilized copper(I) ion in
comparison to 18 [18,25]. This can be explained by the ring current
of the chelating bpy entity. Furthermore, the 1H NMR spectrum of
19 reveals two well separated singlets for the cyclopentadienyl-
bonded Me3Si groups as a result of the different chemical environ-
ment [7a,12b,18].
The identity of 19 was additionally evidenced from mass spectro-
metric investigations. The electrospray ionization mass spectrum of
this compound shows an ion peak at a mass-to-charge ratio (m/z) of
1662.04, which corresponds to [MꢀPF6]+, confirming the elemental
composition and charge state (Section 4).
ꢀ
signal is found for the PF6 counter-ion at ꢀ145.2 ppm with a cou-
3. Conclusion
1
pling constant of JPF = 713 Hz.
The consecutive formation of higher nuclear heterometallic
molecules from 1 is also confirmed by 1H NMR and partly by
13C{1H} NMR spectroscopy since after each individual synthesis
step the resonance signals with the corresponding coupling pat-
terns for the new introduced organic or organometallic fragments
can be seen (Section 4). For example, the protons of the Fc units al-
A series of heteromultimetallic complexes of type 1-(FcC„C)-3-
[(CO)3Cr(
[(CO)3Cr(
g
6-C6H5C„C)]-5-[(Ph3P)AuC„C]C6H3 and [1-(FcC„C)-3-
g
6-C6H5C„C)]-5-[(PPh2)AuC„C-bpy({[Ti](
l-r,p-C„CSiM
e3)2}Cu)]C6H3](PF6) have been synthesized in straightforward con-
secutive synthesis methodologies. This significantly enriches the
family of heteromultimetallic complexes containing early and late

180
R. Packheiser, H. Lang / Inorganica Chimica Acta 366 (2011) 177–183
metal centers. In these molecules three or even five different transi-
tion metal atoms including titanium, chromium, iron, copper and
gold are connected by carbon-rich bridging units based on multi
topic 1,3,5-triethynyl- and 1,3-diethynyl-5-diphenylphosphino-
benzene linking units, respectively. However, due to the high insta-
4.3.2. Synthesis of 1-(Fc-C„C)-3-[(CO)3Cr(
(Me3SiC„C)C6H3 (7)
g
6-C6H5C„C)]-5-
To100 mg(0.166 mmol)of 5and50 mg(0.510 mmol)oftrimeth-
ylsilylacetylene (6) dissolved in 25 mL of Et3N were added 6 mg
(5 mol%) of [(Ph3P)2PdCl2] and 3 mg (10 mol%) of [CuI] at 25 °C. After
stirring this reaction solution for 15 h at 50 °C it was cooled to room
temperature and all volatiles were evaporated in oil-pump vacuum.
The residue was chromatographed on Alox (n-hexane–dichloro-
methane mixture of ratio 3:1, v/v). Complex 7 was obtained as a
yellow–orange solid. Yield: 90 mg (0.146 mmol, 88% based on 5).
Anal. Calc. for C34H26CrFeO3Si (618.5): C, 66.03; H, 4.24. Found:
bility of the [(CO)3Cr(g
6-C6H5C„C)]-containing molecules no
satisfying electrochemical investigations could be carried out.
4. Experimental part
4.1. General data
C, 66.38; H, 4.39%. IR (KBr, cmꢀ1): 2213 (w, mC
„CFc), 2156 (w,
mC„
CSi), 1973, 1890, 1884 (s,
m
CO). 1H NMR (CDCl3): [d] 0.26 (s, 9
All reactions were carried out under an atmosphere of nitrogen
using standard Schlenk techniques. Tetrahydrofuran, diethyl ether,
petroleum ether, n-hexane and n-pentane were purified by distilla-
tion from sodium/benzophenone ketyl; dichloromethane was puri-
fied by distillation from calcium hydride. Celite (purified and
annealed, Erg. B.6, Riedel de Haen) was used for filtrations.
H, SiMe3), 4.25 (s, 5 H, C5H5), 4.26 (pt, JHH = 1.9 Hz, 2 H, C5H4),
4.49 (pt, JHH = 1.9 Hz, 2 H, C5H4), 5.25–5.40 (m, 3 H, C6H5/Cr),
3
4
5.52 (dd, JHH = 6.3 Hz, JHH = 1.0 Hz, 2 H, C6H5/Cr), 7.52 (pt,
JHH = 1.6 Hz, 1 H, C6H3), 7.55 (pt, JHH = 1.6 Hz, 1 H, C6H3), 7.56 (pt,
JHH = 1.6 Hz, 1 H, C6H3).
4.3.3. Synthesis of 1-(Fc-C„C)-3-[(CO)3Cr(
(HC„C)C6H3 (8)
g
6-C6H5C„C)]-5-
4.2. Instruments
Compound 7 (75 mg, 0.121 mmol) was dissolved in 20 mL of
tetrahydrofuran and the thus obtained solution was cooled to
0 °C. Afterwards, 0.15 mL (0.150 mmol) of [nBu4N]F (1 M in tetra-
hydrofuran) were added in a single portion and the reaction solu-
tion was stirred for 1 h at this temperature. After evaporation of all
volatile materials in oil-pump vacuum the obtained residue was
chromatographed on Alox (n-hexane–dichloromethane mixture
of ratio 3:1, v/v), whereby 8 was obtained in form of an orange so-
lid after evaporation of the solvents. Yield: 60 mg (0.110 mmol,
90% based on 7).
Infrared spectra were recorded with a Perkin Elmer FT-IR spec-
trometer, Spectrum 1000. 1H NMR spectra were recorded with a
Bruker Avance 250 spectrometer operating at 250.130 MHz in
the Fourier transform mode; 13C{1H} NMR spectra were recorded
at 62.860 MHz. Chemical shifts are reported in d units (parts per
million) downfield from tetramethylsilane with the solvent as ref-
erence signal (1H NMR: CDCl3, d = 7.26; 13C{1H} NMR: CDCl3,
d = 77.16); 31P{1H} NMR spectra were recorded at 101.255 MHz
in CDCl3 with P(OMe)3 as external standard (d = 139.0, rel. to
H3PO4 (85%) with d = 0.00 ppm). ESI-TOF mass spectra were re-
corded using a Mariner biospectrometry workstation 4.0 (Applied
Biosystems). Microanalyses were performed by the Institute of Or-
ganic Chemistry, Technical University Chemnitz.
Anal. Calc. for C31H18CrFeO3 (546.3): C, 68.16; H, 3.32. Found: C,
67.92; H, 3.47%. IR (KBr, cmꢀ1): 3306 (m,
m
„
C–H), 2213 (m, mC
„CFc),
1970, 1883 (s,
m
CO). 1H NMR (CDCl3): [d] 3.11 (s, 1 H, C„CH), 4.25
(s, 5 H, C5H5), 4.27 (pt, JHH = 1.9 Hz, 2 H, C5H4), 4.51 (pt, JHH = 1.9 Hz,
3
2 H, C5H4), 5.25–5.40 (m, 3 H, C6H5/Cr), 5.53 (dd, JHH = 6.3 Hz,
4JHH = 1.0 Hz, 2 H, C6H5/Cr), 7.54 (pt, JHH = 1.6 Hz, 1 H, C6H3), 7.58
(pt, JHH = 1.6 Hz, 1 H, C6H3), 7.59 (pt, JHH = 1.6 Hz, 1 H, C6H3).
4.3. Reagents
Ethynylferrocene (2) [19], [(CO)3Cr(g
6-C6H5C„CH)] (4) [20], tri-
g
6-C6H5C„C)]-5-
methylsilylacetylene (6) [21], [(Ph3P)AuCl] (9) [22], 1-(FcC„C)-3,5-
4.3.4. Synthesis of 1-(Fc-C„C)-3-[(CO)3Cr(
[(Ph3P)AuC„C]C6H3 (10)
Br2-C6H3 (3)[5a,6e], [(tht)[AuCl](14)[23], 5-ethynyl-2,20-bipyridine
(16) [24] and [{[Ti](l-r,p-C„CSiMe3)2}Cu(N„CMe)]PF6 (18) [25]
To 50 mg (0.092 mmol) of
8 and 45 mg (0.092 mmol) of
were prepared according to published procedures. All other chemi-
cals were purchased from commercial suppliers and were used as
received.
[(Ph3P)AuCl] (9) dissolved in 10 mL of tetrahydrofuran were added
10 mL of Et3N and 1 mg of [CuI] at 25 °C. The reaction mixture was
stirred for 5 h at this temperature, whereby it became turbid. After
all volatile materials have been removed in oil-pump vacuum, the
residue was chromatographed on Alox (diethyl ether–dichloro-
methane mixture of ratio 3:1, v/v). Compound 10 was obtained
as a yellow–orange solid material after evaporation of the solvents.
Yield: 35 mg (0.035 mmol, 38% based on 3).
4.3.1. Synthesis of 1-(Fc-C„C)-3-[(CO)3Cr(
(5)
g
6-C6H5C„C)]-5-Br-C6H3
To 150 mg (0.338 mmol) of 1-(Fc-C„C)-3,5-Br2-C6H3 (3) and
85 mg (0.357 mmol) of [(CO)3Cr(
g
6-C6H5C„CH)] (4) dissolved in
30 mL of Et3N were added 10 mg (5 mol%) of [(Ph3P)2PdCl2] and
5 mg (10 mol%) of [CuI] at 25 °C. The reaction solution was refluxed
for 5 h, cooled to ambient temperature and all volatiles were evap-
orated in oil-pump vacuum. The thus obtained residue was chro-
matographed on Alox (n-hexane–dichloromethane mixture of
ratio 3:1, v/v). The title compound was obtained as an orange solid
material after evaporation of all volatiles. A further band contain-
ing the disubstituted complex was discarded. Yield: 120 mg
(0.200 mmol, 59% based on 3).
Anal. Calc. for C49H32AuCrFeO3P (1004.60): C, 58.58; H, 3.21.
Found: C, 58.76; H, 3.37%. IR (KBr, cmꢀ1): 2210 (m, mC
„
CFc), 2118
(w, mC„CAu), 1969, 1893 (s, m
CO). 1H NMR (CDCl3): [d] 4.25 (s, 5
H, C5H5), 4.27 (pt, JHH = 1.9 Hz, 2 H, C5H4), 4.50 (pt, JHH = 1.9 Hz, 2
3
H, C5H4), 5.25–5.40 (m, 3 H, C6H5/Cr), 5.52 (dd, JHH = 6.3 Hz,
4JHH = 1.0 Hz, 2 H, C6H5/Cr), 7.40–7.65 (m, 15 H (C6H5) + 3 H
(C6H3)). 31P{1H} NMR (CDCl3): [d] 41.1 (s, AuPPh2).
4.3.5. Synthesis of 1-(Fc-C„C)-3-Br-5-(PPh2)C6H3 (12)
Anal. Calc. for C29H17BrCrFeO3 (601.20): C, 57.94; H, 2.85.
To 2.0 g (4.51 mmol) of 1-(FcC„C)-3,5-Br2-C6H3 (3) in 60 mL of
tetrahydrofuran were slowly added (20 min) 2.80 mL (4.50 mmol)
of n-BuLi (1.6 M in n-hexane) at ꢀ80 °C. Afterwards, the reaction
solution was stirred for 2 h at this temperature. Then 1.10 g
(4.99 mmol) of chlorodiphenylphosphine (11) were drop-wise
added and the cooling bath was removed. After the reaction solution
reached room temperature 1 mL of ethanol was added in a single
Found: C, 57.69; H, 3.09%. IR (KBr, cmꢀ1): 2213 (w, mC
„
CFc),
CO). 1H NMR (CDCl3): [d] 4.25 (s, 5 H, C5H5),
4.28 (pt, JHH = 1.9 Hz, 2 H, C5H4), 4.51 (pt, JHH = 1.9 Hz, 2 H, C5H4),
1973, 1890, 1878 (s,
m
3
4
5.25–5.40 (m, 3 H, C6H5/Cr), 5.52 (dd, JHH = 6.2 Hz, JHH = 1.0 Hz,
H, C6H5/Cr), 7.55 (pt, JHH = 1.6 Hz, H, C6H3), 7.57 (pt,
JHH = 1.6 Hz, 1 H, C6H3), 7.61 (pt, JHH = 1.6 Hz, 1 H, C6H3).
2
1

R. Packheiser, H. Lang / Inorganica Chimica Acta 366 (2011) 177–183
181
portion and all volatiles were evaporated in oil-pump vacuum. The
thus obtained residue was dissolved in diethyl ether (50 mL) and
was filtered through a pad of Celite to remove LiBr. After all volatiles
were evaporated, the obtained residue was chromatographed on
Alox (diethyl ether–tetrahydrofuran mixture of ratio 8:1, v/v). Com-
pound 12 was obtained as an orange–red solid material after evapo-
ration of the solvents. Yield: 2.08 g (3.79 mmol, 84% based on 3).
Anal. Calc. for C30H22BrFeP (549.23): C, 65.61; H, 4.04. Found: C,
stirring at 25 °C all volatile materials were evaporated in oil-pump
vacuum and the residue was chromatographed on Alox (tetrahy-
drofuran–n-hexane 1:1, v/v). Molecule 17 was eluted as an orange
band. After removal of all volatiles, complex 17 was obtained as an
orange solid in 72% yield (50 mg, 0.046 mmol, based on 15).
Anal. Calc. for C53H34AuCrFeN2O3P (1082.65): C, 58.80; H, 3.17; N,
2.59. Found: C, 58.99; H, 3.56; N, 2.42%. IR (KBr, cmꢀ1): 2211 (m,
mC„CFc), 2116 (w, mC„CAu), 1970, 1897 (s, m
CO). 1H NMR (CDCl3): [d]
65.14; H, 4.17%. IR (KBr, cmꢀ1): 2207 (m, mC
„
CFc). 1H NMR (CDCl3):
4.25 (s, 5 H, C5H5), 4.27 (pt, JHH = 1.9 Hz, 2 H, C5H4), 4.50 (pt,
[d] 4.27 (s, 5 H, C5H5), 4.29 (pt, JHH = 1.9 Hz, 2 H, C5H4), 4.53 (pt,
JHH = 1.9 Hz, 2 H, C5H4), 7.36–7.46 (m, 10 H (C6H5), 2 H (C6H3)),
7.66 (pt, JHH = 1.6 Hz, 1 H, C6H3). 13C{1H} NMR (CDCl3): [d] 64.4
(Ci/C5H4), 69.2 (CH/C5H4), 70.1 (C5H5), 71.6 (CH/C5H4), 84.2
JHH = 1.9 Hz, 2 H, C5H4), 5.25–5.38 (m, 3 H, C6H5/Cr), 5.52 (dd,
3
JHH = 6.3 Hz, 4JHH = 1.0 Hz, 2 H, C6H5/Cr), 7.27 (ddd, 3JH5 H4 = 7.8 Hz,
0
0
3
4
JH5 H6 = 4.7 Hz, JH5 H3 = 1.0 Hz, 1 H, H50/bpy), 7.44–7.65 (m, 10 H
0
0
0
0
(C6H5) + 2 H (C6H3)), 7.74 (dpt, JHP = 1.4 Hz, JHH = 1.6 Hz, 1 H, C6H3),
3
3
4
(C„C), 90.9 (C„C), 122.8 (d, JCP = 6.5 Hz, Ci/C6H3), 126.2 (d,
7.79 (ddd, JH4 H3 = 3JH4 H5 = 7.8 Hz, JH4 H6 = 1.7 Hz, 2 H, H40/bpy),
0
0
0
0
0
0
3
3
4
3JCP = 8.0 Hz, Ci/C6H3), 128.8 (d, JCP = 7.1 Hz, Cm/C6H5), 129.3 (Cp/
7.91 (dd, JH4H3 = 8.2 Hz, JH4H6 = 2.2 Hz, 2 H, H4/bpy), 8.32 (dd,
2
2
C6H5), 133.9 (d, JCP = 20.0 Hz, Co/C6H5), 134.1 (d, JCP = 4.5 Hz,
3JH3H4 = 8.2 Hz, 5JH3H6 = 0.6 Hz,
2
H, H3/bpy), 8.38 (ddd,
2
3
3
4
JH3 H4 = 7.8 Hz, JH3 H5 = 5JH3 H6 = 1.0 Hz, 2 H, H30/bpy), 8.66 (ddd,
0
0
0
0
0
0
CH/C6H3), 134.7 (d, JCP = 4.7 Hz, CH/C6H3), 135.1 (CH/C6H3), 136.0
(d, JCP = 11.0 Hz, Ci/C6H5), 140.7 (d, JCP = 17.2 Hz, Ci/C6H3).
JH6 H5 = 4.7 Hz, JH6 H4 = 1.7 Hz, JH6 H3 = 1.0 Hz, 2 H, H60/bpy),
1
1
4
5
0
0
0
0
0
0
31P{1H} NMR (CDCl3): [d] ꢀ5.6 (s, PPh2).
8.82 (dd, 4JH6H4 = 2.2 Hz, 5JH6H3 = 0.6 Hz, 2 H, H6/bpy). 31P{1H} NMR
(CDCl3): [d] 41.4 (s, AuPPh2).
4.3.6. Synthesis of 1-(Fc-C„C)-3-[(CO)3Cr(
(PPh2)C6H3 (13)
g
6-C6H5C„C)]-5-
4.3.9. Synthesis of [1-(Fc-C„C)-3-[(CO)3Cr(g
6-C6H5C„C)]-5-
To 150 mg (0.273 mmol) of 12 and 70 mg (0.294 mmol) of 4 in
30 mL of triethylamine were added 10 mg (5 mol%) of [(PPh3)2PdCl2]
and 5 mg (10 mol%) of [CuI] in a single portion. The thus obtained
reaction mixture was heated for 15 h to reflux. After cooling to room
temperature all volatiles were removed in vacuum and the residue
was purified by column chromatography (Alox, n-hexane–tetrahy-
drofuran mixture of ratio 3:1, v/v). After un-reacted starting materi-
als were removed, an orange band could be eluted from which
complex 13 could be separated as an orange solid material after re-
moval of the solvents. Yield: 45 mg (0.064 mmol, 23% based on 12).
Anal. Calc. for C41H27CrFeO3P (706.48): C, 69.71; H, 3.85. Found:
[(PPh2)AuC„C-bpy-Cu-{(Me3SiC„C)2[Ti]}]C6H3]PF6 (19)
To 40 mg (0.061 mmol) of 17 were dissolved in 15 mL of tetra-
hydrofuran and 95 mg (0.124 mmol) of [{[Ti](l-r,p-C„CSiM-
e3)2}Cu(N„CMe)]PF6 (18) were added in a single portion. After
2 h of stirring at 25 °C the color of the reaction solution was red.
Afterwards, the solvent was reduced in oil-pump vacuum to 3 mL
and then 20 mL of n-hexane were added whereby 19 precipitated.
Washing the residue twice with 10 mL portions of diethyl ether
and trying the solid in oil-pump vacuum gave 19 as an orange solid
material in 86% yield (145 mg, 0.053 mmol, based on 17).
Anal. Calc. for
C79H78AuCrCuF6FeN2O3P2Si4Ti (1808.00): C,
C, 69.23; H, 4.14%. IR (KBr, cmꢀ1): 2210 (m, mC
CO). 1H NMR (CDCl3): [d] 4.22 (s, 5 H, C5H5), 4.24 (pt, JHH = 1.9 Hz, 2
H, C5H4), 4.47 (pt, JHH = 1.9 Hz, 2 H, C5H4), 5.22–5.38 (m, 3 H, C6H5/
„CFc), 1971, 1897 (s,
52.48; H, 4.35; N, 1.55. Found: C, 52.14; H, 4.72; N, 1.45%. IR
(KBr, cmꢀ1): 2210 (m, mC
m
„CFc), 2118 (w, mC„CAu), 1970, 1896, (s,
m
CO). 1H NMR (CDCl3): [d] ꢀ0.51 (s, 18 H, SiMe3), 0.27 (s, 9 H, SiMe3),
3
4
Cr), 5.49 (dd, JHH = 6.5 Hz, JHH = 1.0 Hz, 2 H, C6H5/Cr), 7.29–7.43
(m, 10 H (C6H5), 2 H (C6H3)), 7.60 (pt, JHH = 1.6 Hz, 1 H, C6H3).
31P{1H} NMR (CDCl3): [d] ꢀ6.2 (s, PPh2).
0.28 (s, 9 H, SiMe3), 4.23 (s, 5 H, C5H5), 4.27 (br s, 2 H, C5H4), 4.49
(br s, 2 H, C5H4), 5.26–5.39 (m, 3 H, C6H5/Cr), 5.51 (d, JHH = 6.0 Hz,
2 H, C6H5/Cr), 6.27 (br s, 8 H, C5H4Si), 7.41–7.77 (m, 10 H (C6H5) + 3
H (C6H3) + 1 H (H5/bpy)), 8.13–8.27 (m, 2 H, H4,H40/bpy), 8.40 (d,
JHH = 8.2 Hz, 1 H, H3/bpy), 8.47–8.57 (m, 3 H, H30,H6,H60/bpy).
4.3.7. Synthesis of 1-(Fc-C„C)-3-[(CO)3Cr(
[(PPh2)AuCl]C6H3 (15)
g
6-C6H5C„C)]-5-
31P{1H} NMR (CDCl3): [d] ꢀ145.2 (septett, JPF = 713 Hz, PF6), 41.2
1
(s, AuPPh2). ESI MS (m/z): 1662.04 ([MꢀPF6]+).
To 30 mg (0.094 mmol) of [(tht)AuCl] (14) dissolved in 10 mL of
tetrahydrofuran was added at 0 °C during 20 min a solution of
70 mg (0.099 mmol) of 13 in 10 mL of tetrahydrofuran. Afterwards,
the cooling bath was removed and the reaction mixture was stirred
for 1 h at ambient temperature, and was than filtered through a
pad of Celite. The volume of the solution was concentrated to 2–
3 mL and than 15 was precipitated by addition of 20 mL of n-hex-
ane. The obtained orange solid material was washed twice with
10 mL portions of n-hexane and was than dried in oil-pump vac-
uum. Yield: 68 mg (0.072 mmol, 77% based on 13).
Acknowledgements
We are grateful to the Deutsche Forschungsgemeinschaft (DFG)
and the Fonds der Chemischen Industrie (FCI) for generous finan-
cial support of this work.
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