Mixed-transition-metal acetylides: Synthesis and characterization of complexes with up to six different transition metals connected by carbon-rich bridging units

Article abstract of DOI:10.1002/chem.200701915

The synthesis and reaction chemistry of heteromultimetallic transition-metal complexes by linking diverse metal-complex building blocks with multifunctional carbon-rich alkynyl-, benzene-, and bipyridyl-based bridging units is discussed. In context with this background, the preparation of [1-{(η²-dppf)(η⁵-C₅H ₅)RuC=C)-3-{(tBu₂bpy)(CO)₃ReC≡C}-5- (PPh₂)-C₆H₃] (10) (dppf=1,1′- bis(diphenyl-phosphino)ferrocene; tBu₂bpy = 4,4′-diferi-butyl- 2,2′-bipyridyl; Ph = phenyl) is described; this complex can react further, leading to the successful synthesis of heterometallic complexes of higher nuclearity. Heterotetrametallic transition-metal compounds were formed when 10 was reacted with [((η⁵-C₅Me₅)-RhCl ₂}₂] (18), [(Et₂S)₂PtCl₂] (20) or -(tht)AuC≡C-bpy] (24) (Me = methyl; Et = ethyl ; tht = tetrahydrothiophene ; bpy = 2,2′-bipyridyl-5-yl). Complexes [1-((η²-dppf)(η⁵-C₅H ₅)RuC=C}-3-{(tBu₂bpy)(CO)₃ReC≡C)-5- (PPh₂RhCl₂(η⁵-C₅Me ₅)C₆H₃] (19), [{1-[(η²-dppf) (η⁵-C₅H₅)RuC=C]-3-[(tBu₂-bpy) (CO).,ReC=-C]-5-(PPh₂)C₆H₃}_2- PtCl₂] (21), and [1-((η²-dppf)(η⁵- C₅H₅)-RuC≡C}-3-((tBu₂bpy)(CO) ₃ReC≡C)-5-(PPh₂AuC≡C-bpy)C₆H ₃] (25) were thereby obtained in good yield. After a prolonged time in solution, complex 25 undergoes a transmetallation reaction to produce [(tBu₂bpy)(CO)₃ReC≡C-bpy] (26). Moreover, the bipyridyl building block in 25 allowed the synthesis of Fe-Ru-Re-Au-Mo- (28) and Fe-Ru-Re-Au-Cu-Ti-based (30) assemblies on addition of [(nbd)Mo(CO) ₄] (27), (nbd = 1,5-norbornadiene), or [{[Ti](μ-σ,π- C≡CSiMe₃)₂)Cu(N=CMe)]-[PF₆] (29) ([Ti] = (η⁵-C₅H₄SiMe₃)₂Ti) to 25. The identities of 5, 6, 8, 10-12, 14-16, 19, 21, 25, 26, 28, and 30 have been confirmed by elemental analysis and IR, ¹H, ¹³C{ ¹H}, and ³¹P{¹H} NMR spectroscopy. From selected samples ESI-TOF mass spectra were measured. The solid-state structures of 8, 12, 19 and 26 were additionally solved by single-crystal X-ray structure analysis, confirming the structural assignment made from spectroscopy.

Full text of DOI:10.1002/chem.200701915

DOI: 10.1002/chem.200701915
Mixed-Transition-Metal Acetylides: Synthesis and Characterization of
Complexes with up to Six Different Transition Metals Connected by
Carbon-Rich Bridging Units
Rico Packheiser, Petra Ecorchard, Tobias Rüffer, and Heinrich Lang*[a]
ꢁ
Abstract: The synthesis and reaction
chemistry of heteromultimetallic transi-
tion-metal complexes by linking di-
verse metal-complex building blocks
with multifunctional carbon-rich alkyn-
yl-, benzene-, and bipyridyl-based
bridging units is discussed. In context
with this background, the preparation
[(tht)AuC C-bpy] (24) (Me=methyl;
Et=ethyl; tht=tetrahydrothiophene;
bpy] (26). Moreover, the bipyridyl
building block in 25 allowed the syn-
thesis of Fe-Ru-Re-Au-Mo- (28) and
Fe-Ru-Re-Au-Cu-Ti-based (30) assem-
blies on addition of [(nbd)Mo(CO)4]
(27), (nbd=1,5-norbornadiene), or
bpy=2,2’-bipyridyl-5-yl).
Complexes
[1-{(h2-dppf)
{(tBu2bpy)(CO)3ReC C}-5-
{PPh2RhCl2
(h5-C5Me5)}C6H3] (19), [{1-
(h5-C5H5)Ru
C C}-3-
G
ꢁ
ꢁ
AHCTREUNG
[(h2-dppf)
bpy)(CO)3ReC C]-5-(PPh2)C6H3}2-
PtCl2] (21), and [1-{(h2-dppf)(h5-C5H5)-
A
[{[Ti](m-s,p-C CSiMe3)2}Cu
C
5
ꢁ
ꢁ
ꢁ
ꢁ
U
ACHTREUNG
5
of
[1-{(h2-dppf)
G
A
N
25. The identities of 5, 6, 8, 10–12, 14–
16, 19, 21, 25, 26, 28, and 30 have been
confirmed by elemental analysis and
IR, 1H, 13C{1H}, and 31P{1H} NMR spec-
troscopy. From selected samples ESI-
TOF mass spectra were measured. The
solid-state structures of 8, 12, 19 and 26
were additionally solved by single-crys-
tal X-ray structure analysis, confirming
the structural assignment made from
spectroscopy.
ꢁ
ꢁ
ꢁ
{(tBu2bpy)(CO)3ReC C}-5-(PPh2)-
RuC C}-3-{(tBu2bpy)(CO)3ReC C}-5-
ꢁ
C6H3] (10) (dppf=1,1’-bis(diphenyl-
{PPh2AuC C-bpy}C6H3] (25) were
thereby obtained in good yield. After a
prolonged time in solution, complex 25
undergoes a transmetallation reaction
phosphino)ferrocene; tBu2bpy=4,4’-di-
tert-butyl-2,2’-bipyridyl; Ph=phenyl) is
described; this complex can react fur-
ther, leading to the successful synthesis
of heterometallic complexes of higher
nuclearity. Heterotetrametallic transi-
tion-metal compounds were formed
when 10 was reacted with [{(h5-C5Me5)-
ꢁ
to produce [(tBu2bpy)(CO)3ReC C-
Keywords: heterometallic
plexes · mass spectrometry · solid-
state structures · transition metals
com-
A
Introduction
semblies requires the accessibility of multitopic bridging
units featuring diverse reactive coordination sites.[1,2] In this
respect, metal-containing alkynyls have been studied exten-
sively due to their rigid structures, their stability, and, for ex-
ample, their rich spectroscopic, photophysical, and electro-
chemical properties.[2] To control the structure and composi-
tion of multimetallic complexes, a prior synthesis of multi-
functional bridging ligands is necessary that allows the step-
wise metal coordination. Examples of such connectivities
are 1,4-diethynylbenzene,[3,4] 1,3,5-triethynylbenzene,[5,6] 1-
ethynyl-4-diphenylphosphinobenzene,[7] 5-ethynyl-2,2’-bipyr-
The linkage of transition-metal complexes to give (hetero)-
multimetallic species is, from the viewpoint of synthetic
chemistry, a challenge, since the molecular design of such as-
[a] Dipl.-Chem. R. Packheiser, Dr. P. Ecorchard, Dr. T. Rüffer,
Prof. Dr. H. Lang
Fakultät für Naturwissenschaften, Institut für Chemie
Lehrstuhl für Anorganische Chemie
Technische Universität Chemnitz
Strasse der Nationen 62, 09111 Chemnitz (Germany)
Fax : (+49)371-531-21219
E-mail: heinrich.lang@chemie.tu-chemnitz.de
idyl,[8] and 2,5-bis(alkynyl) thiophenes.[9,10] Based on these
G
cores, mainly homometallic transition-metal compounds
have been synthesized, while less is known about heteromul-
timetallic molecules. Recently, Long and Yam reported a
series of phenylenethynyl-bridged di- and trinuclear com-
Supporting information for this article is available on the WWW
under http://www.chemeurj.org/ or from the author. It contains a de-
scription of the structure of complex 26 in the solid state (Figure S1)
and discussion of the 2D layers formed by p–p interactions (Figur-
es S2 and S3), including the crystallographic data (Table S1).
ꢀ
ꢀ
ꢀ
ꢀ
plexes featuring Re Pt, Re Pd2, and Fe Ru Os metal
4948
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Chem. Eur. J. 2008, 14, 4948 – 4960

FULL PAPER
atoms.[4a,6b,c]
Electrochemical
and luminescence studies were
carried out on these rigid-rod-
structured compounds.
Very recently, we reported
on the synthesis of heterodi-[11]
and heterotrimetallic com-
pounds[8a,12] in which early and
late transition-metal atoms are
spanned by carbon-rich p-con-
jugated connectivities. These
molecules showed a novel reac-
tivity and reaction chemistry compared with that of related
mononuclear complexes. Within these studies, heterotetra-
metallic[12a,b,13] and even heteropentametallic[7b,c] transition-
metal complexes could be synthesized and structurally char-
acterized by our group for the first time. As multitopic link-
ing units, for example, 5-ethynyl-2,2’-bipyridyl and 1-ethyn-
yl-4-diphenylphosphino benzene were used. Extending the
core into three directions (e.g., a type A molecule) is of in-
ꢁ
Scheme 1. Synthesis of 5: i)
[(Ph3P)2PdCl2]/
ꢀ808C; 2. ClPPh2, Et2O, ꢀ80!258C.
1
.nBuLi, Et2O, ꢀ908C; 2. I2, Et2O/Thf, ꢀ90!258C; ii) HC CSiMe3,
[CuI], Thf/NEt3, 08C; iii) 1. tBuLi, Et2O, ꢀ808C; 2. I2, Et2O, ꢀ80!258C; iv) 1. nBuLi, Et2O,
acetylene (synthesis of 3; Scheme 1).[5j] Lithiation of 4 with
nBuLi and treatment of Li-4 with equimolar amounts of
chlorodiphenylphosphine gave 5 in good yield (Scheme 1).
Scheme 2 shows the reaction scheme involving com-
pounds 5–9 to successfully give [1-{(h2-dppf)
ACHTREUNG
ꢁ
ꢁ
RuC C}-3-{(tBu2bpy)(CO)3ReC C}-5-(PPh2)C6H3]
(dppf=1,1’-bis(diphenylphosphino)ferrocene;
4,4’-di-tert-butyl-2,2’-bipyridine; Ph=phenyl). Desilylation
of 5 afforded 1-ethynyl-3-iodo-5-diphenylphosphinobenzene
(6), which was further treated with [(h2-dppf)(h5-
G
C5H5)RuCl] (7) in refluxing methanol followed by the addi-
tion of sodium metal to give 8 (Scheme 2). This procedure,
adapted from that of Field et al.,[14] was preferred over the
method using [NH4]PF6 and DBU (DBU=1,8-diazabicyclo-
A
ꢁ
yields of 8. Reacting 8 with [(tBu2bpy)(CO)3ReC CH] (9)
under typical Sonogashira cross-coupling reaction conditions
produced orange heterotrimetallic 10 (Scheme 2).
After the appropriate workup, complex 10 could be isolat-
ed in very low yield. The limiting step in the synthesis of 10
is the low turnover of the Sonogashira carbon–carbon cross-
coupling reaction and the thereby partial decomposition of
8 under the reaction conditions used (i.e., refluxing triethyl-
terest, since such species should serve as versatile building
blocks allowing carbon-rich molecules of higher nuclearity
to be synthesized.
amine). Since 10 is the key metal precursor for the synthesis
In particular, molecule A should be able to exploit the
electron-based cooperation between individual transition-
metal subunits of molecular assemblies with a delocalized p-
backbone. This may allow diverse applications in material
sciences to be found.
of higher heteromultimetallic molecules [see Eq. (1)] and
Scheme 4 below) another and, hence, more efficient and
straightforward way to prepare this compound had to be de-
veloped.
The better synthetic approach used to synthesize 10 is
based on the reaction sequence 5!11!12!10 as depicted
in Scheme 2. It was found that the reaction of organic 5 with
9 gave somewhat better yields than with 8 with 9. Desilyl-
Here, we describe a series of novel heteromultimetallic
complexes with up to six different transition metals (Ti, Re,
Fe, Ru, Cu, and Au) based on the 1,3-bis(ethynyl)-5-diphe-
A
nylphosphinobenzene core as a linking unit.
ACHTREUNG
AHCTREUNG
Results and Discussion
[NH4]PF6 and DBU (see above) produced 10 only in moder-
ate yield. In summary, the over-all yield of the second reac-
tion route was admittedly better then the first one, but still
not satisfactory.
The choice of these two reaction routes finally leading to
10 was determined by the desire to prevent side products,
because the respective reactions should preferentially give
the postulated compounds. The introduction of the rheni-
Synthesis and spectroscopic analysis: Scheme 1shows the
transformation of compound 1 through 2–4 to give the start-
ing material 1-trimethylsilylethynyl-3-iodo-5-diphenylphos-
phinobenzene (5). In detail, compound 5 was synthesized
from 1,3-diiodo-5-trimethylsilylethynylbenzene (4), which
was accessible by using consecutive reactions including
halide exchange reactions (synthesis of 2 and 4) and Sonoga-
shira carbon–carbon cross coupling of 2 with trimethylsilyl-
AHCTREUNG
Chem. Eur. J. 2008, 14, 4948 – 4960
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www.chemeurj.org
4949

H. Lang et al.
nylphosphino benzene (15)
(Scheme 3). Alternatively, the
reaction of 13 with 2-methyl-3-
butyn-2-ol (formation of 16)
under
typical
Sonogashira
cross-coupling conditions also
gave 15 (Scheme 3).[15] Desilyl-
ation of 14 was achieved by ad-
dition of [nBu4N]F. The de-pro-
tection of the propargylic group
in 16 was carried out with pow-
dered potassium hydroxide in
toluene. Both reactions pro-
duced 15 as a colorless solid in
good yield.
The introduction of the first
transition-metal building block
in 15 succeeded by mono-lithia-
tion of 15 with one equivalent
of LiN
in toluene at room temperature
followed by addition of
[(tBu2bpy)(CO)3ReCl] (17) and
heating the reaction mixture to
reflux (Scheme 3). This new
procedure allowed the isolation
A
Scheme 2. Synthesis of trimetallic 10 from 5: i) [nBu4N]F, Thf, 258C; ii) 1. [(h2-dppf)
ACHTREUNG
ꢁ
MeOH, reflux; 2. Na, MeOH, 258C; iii) [(tBu2bpy)(CO)3ReC CH] (9), [(Ph3P)2PdCl2]/
ACHTREUNG
iv) 1. [(h2-dppf)
A
strated to be possible, but, unfortunately, proved to be un-
suitable in this case because of very low yields obtained
under the reaction conditions used.
In contrast, the most straightforward and efficient meth-
odology to synthesize 10 starts from the reaction of 1,3-di-
bromo-5-diphenylphosphino-benzene (13) with trimethyl-
silylacetylene (formation of 14) under typical Sonogashira
of 12 in about 45% yield. Nevertheless, this reaction did not
take place when diethyl ether, tetrahydrofuran, or mixtures
of both were used.[16] This behavior is most probably attrib-
uted to the low solubility of 17 in diethyl ether and to the
observation that Li-15 decomposed quite fast in tetrahydro-
furan. Also the methods introduced by Yam et al. and PØrez
et al. using the reaction of the rhenium chloride precursor
with terminal acetylides in the presence of [AgOTf] (OTf=
cross-coupling conditions to give 1,3-bis(ethynyl)-5-diphe-
G
ꢁ
ꢁ
Scheme 3. Synthesis of 10 from 13: i) HC CSiMe3, [(Ph3P)2PdCl2]/
[CuI], HNiPr2, reflux; ii) [nBu4N]F, Thf, 258C; iii) HC CCMe2OH,
[(Ph3P)2PdCl2]/
dppf)
A
H
(h5-C5H5)RuCl] (7), [NH4]PF6, KOtBu, CH2Cl2/MeOH, 258C.
4950
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Mixed-Transition-Metal Acetylides
FULL PAPER
1
trifluoromethanesulfonate) and NEt3 (Et=ethyl) in reflux-
ing tetrahydrofuran and the reaction of [(bpy)(CO)3Re-
troscopy and also from H NMR studies due to a second set
of resonance signals.
A
G
A possibility to introduce a transition-metal fragment
with a further coordination site allowing the incorporation
of other metal building blocks should be possible using the
successive reaction of 10 with [(tht)AuCl] (tht=tetrahydro-
thiophene) (22) and 5-ethynyl-2,2’-bipyridyl (23).[13a,18] Thus,
10 was treated with 22 in tetrahydrofuran. After the appro-
priate workup, including column chromatography,
[(tBu2bpy)(CO)3ReCl] could be isolated as the only un-
equivocally characterized molecule including X-ray struc-
ture analysis.[16b] This observation corresponds to an unex-
pected transmetallation reaction between the gold and rhe-
nium atoms.
chloromethane/methanol mixture with the simultaneous ad-
dition of [NH4]PF6 and the base KOtBu (OtBu=tert-butan-
ACHTREUNGolACHTREUNG
nicely in polar organic solvents. However, in solution it is
observed that 10 is easier to oxidize at the phosphorus atom
than, for example, triphenylphosphine, giving the appropri-
ate phosphinoxide. Due to this, oxygen must strictly be ex-
cluded during the workup procedure.
The Fe-Ru-Re compound 10 bears a free PPh2 group that
is able to react with a fourth transition-metal fragment to
form heterotetranuclear molecules in which four different
Another widely used method for the preparation of new
phosphine gold(I) acetylide complexes centers on the depo-
lymerization reaction of neutral homoleptic gold(I) poly-
ꢁ
metals are connected by the bis
phosphinobenzene core.
Cleavage of the chloride-bridged dimer [{(h5-C5Me5)-
RhCl2}2] (18) upon addition of 10 in dichloromethane
at 258C leads to the formation of [1-{(h2-dppf)(h5-
(h5-
C6H3] (19) (Scheme 4). Pure 19 was obtained as a
C
di
G
mers of the type [{AuC CR}n] upon addition of tertiary
phosphines. Such reactions enabled the synthesis of a high
E
number of neutral[19] and ionic gold(I) alkynyl deriva-
ꢁ ꢀ
N
tives.[20,21] In this context, we tried to prepare [{AuC C
bpy}n] by reacting 5-ethynyl-2,2’-bipyridyl (23) with
[(tht)AuCl] (22) in the presence of triethylamine. However,
this reaction did not result in the precipitation of the desired
polymeric species. Furthermore, the addition of catalytic
amounts of CuI only led to the decomposition and forma-
tion of elemental gold.
For this reason we treated [(tht)AuCl] (22) with 5-ethyn-
yl-2,2’-bipyridyl (23) in a tetrahydrofuran/diethylamine mix-
ture. The addition of catalytic amounts of CuI to this reac-
tion mixture led to a turbidity, which was attributed to the
formation of HNEt2 ”HCl. However, attempts to isolate the
formed product failed due to its instability, which was not
unexpected since thioether-sub-
ꢁ
ꢁ
ACHTREUNG
red crystalline material in 86% yield by precipitation from
dichloromethane with n-hexane.
The reaction of 10 with 0.5 equivalents of [(Et2S)2PtCl2]
(20) produced, upon replacement of both diethylsulfide li-
gands with the tertiary phosphine 10, the heptametallic com-
plex 21 which possesses a trans-configuration (Scheme 4). A
small amount (ca. 5%) of the isomer containing the cis-[Pt-
(PR3)2Cl2] fragment was evidenced from 31P{1H} NMR spec-
stituted gold(I) acetylides have
not been reported so far. Nev-
ertheless, we suggest the main
product
to
be
[(tht)Au
ꢁ
C C-bpy] (24). Another possi-
bility is that in this reaction the
alkynyl ligand and the amine
itself replace both the tht and
the chloride ligand, forming
ꢁ
[(HNEt2) uC C-bpy], which
G
could be shown by Vicente
ꢁ
et al. for [(HNEt2)AuC CR]
(R=SiMe3, tBu).[21] Since 24
could not be isolated this as-
sumption could not be con-
firmed. Thus, in situ prepared
24 was reacted with the tertiary
phosphine 10 to give the de-
sired Fe-Ru-Re-Au transition-
metal complex 25 after column
chromatography in good yield
[Eq. (1)].
Scheme 4. Synthesis of 19 and 21 from 10.
Chem. Eur. J. 2008, 14, 4948 – 4960
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4951

H. Lang et al.
When trying to crystallize 25 by diffusion of n-hexane into
a solution of 25 in dichloromethane, it appeared that this
complex was not stable for a long period of time. Complex
The identities of 5, 6, 8, 10–12, 14–16, 19, 21, 25, 26, 28,
and 30 have been confirmed by elemental analysis, infrared
(IR) spectroscopy, and 1H, 31P{1H} and partly by 13C{1H}
NMR spectroscopy. From selected samples the electrospray
ionization time of flight (ESI-TOF) mass spectra were mea-
sured. The solid-state structures of 8, 12, 19 and 26 were ad-
ditionally solved by single-crystal X-ray structure analysis,
thus confirming the structural assignment made from spec-
troscopic analysis.
ꢁ
25 decomposed to produce [(tBu2bpy)(CO)3ReC C-bpy]
(26) along with an insoluble yellow precipitate, which does
not dissolve in common organic solvents. This observation
again underlies an unexpected transmetallation reaction be-
tween the Re and Au alkynyls. The transmetallation product
was indisputably characterized by single-crystal X-ray dif-
fraction studies. The insoluble precipitate probably evinces a
polymeric structure formed by the remaining phosphine
gold(I) acetylide building block.
Most characteristic in the IR spectra of all complexes are
the nCꢁ and nCO vibrations which are diagnostic and repre-
C
sent a useful monitoring tool. However, it should be noted
Nevertheless, complex 25 with its four different transition-
metal atoms is the key starting material for the synthesis of
organometallic molecules of higher nuclearity, due to the
presence of a pendant 2,2’-bipyridyl entity as a further N-li-
gating site. Thus, complex 25 was reacted with equimolar
amounts of [(nbd)Mo(CO)4] (27) (nbd=2,5-norbornadiene)
in a 5:1mixture of dichloromethane/tetrahydrofuran at
258C to obtain the respective heteropentanuclear Fe-Ru-
that the intensity of the nCꢁ vibrations can vary so that in
some of the complexes not all of the expected bands can be
C
detected. As an example, this is shown for the series 5!8!
10!25!30. While the nCꢁ absorption band for 5 is found
C
at 2150 cmꢀ1, it is shifted to 2055 and 2065 cmꢀ1 in 8 and 10,
respectively. This observation nicely reflects the introduction
of a ruthenium(II) entity and is representative in transition-
metal–acetylide chemistry.[22] The difference of the nCꢁ
C
Re-Au-Mo compound. Admittedly, the expected complex
bands in 8 and 10 by 10 cmꢀ1 mirrors a weak interaction be-
5
[1-{(h2-dppf)
A
tween the ruthenium and rhenium atoms through the
ꢁ
ꢁ
ꢁ
ꢁ
[PPh2AuC C-bpy{Mo(CO)4}]C6H3] (28) could not be isolat-
ed in a pure form; this fact is attributed to the partial de-
composition of 25 during the long reaction time of 15 h. In
contrast, when 25 was treated with the organometallic p-
carbon-rich connectivity. The ReC C stretching frequency,
ꢁ
however, overlaps with the RuC C band. In 25 an addition-
al vibration is found at 2116 cmꢀ1 for the AuC C unit.
[19–21]
ꢁ
The [(tBu2bpy)Re(CO)3] fragment is evidenced by the pres-
ence of three intense carbonyl stretching modes between
1900–2005 cmꢀ1 as expected for a [M(CO)3] building block
in a facial arrangement.[6b,16] Due to this, the predictable
ꢁ
ꢁ
tweezer [{[Ti](m-s,p-C CSiMe3)2}Cu(N CMe)]PF6 (29) in
A
tetrahydrofuran heterohexanuclear 30 was formed in a
straightforward manner, that is, the acetonitrile is substitut-
ed by the bipyridyl ligand [Eq. (2)]. In this reaction, the co-
ordination number at copper is changed from three (planar)
to four (tetrahedral).[8a,11]
weak nCꢁ
vibration at titanium (expected at ca.
C
1925 cmꢀ1)[8a,11] in 30 is covered.
4952
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Chem. Eur. J. 2008, 14, 4948 – 4960

Mixed-Transition-Metal Acetylides
FULL PAPER
The 31P{1H} NMR spectra of 5, 6, 11, 12, and 14–16 indi-
cate the presence of a single phosphorus environment. In all
other complexes in which the {(h2-dppf)(h5-C5H5)Ru} unit is
N
present, a second resonance signal is observed at about
54 ppm.[23] The chemical shift of the benzene-bonded PPh2
entity is almost independent (ꢀ5 to ꢀ6 ppm) of the appro-
priate substitution pattern of the benzene core, while a rep-
resentative shift to lower field takes place upon coordination
to a transition-metal fragment as given in 19, 21, 25, 28, and
30. For example, the coordination of the tertiary phosphine
10 to a {RhCl
2(h5-C5Me5)} fragment is best reflected by a
G
downfield shift to 29.8 ppm (19). The resonance signal there-
by shows a characteristic coupling with 103Rh (I=1= , 100%
2
abundance) giving a doublet with a typical J(31P, 103Rh) cou-
1
Figure 1. ESI MS spectrum of heterohexametallic 30.
pling constant of 144 Hz.[24]
The consecutive building of higher nuclear heterometallic
1
molecules from 5 and 15 is also confirmed by H and partly
spective dichloromethane or chloroform solutions. The
solid-state structures together with selected bond lengths
(Š) and angles (8) are presented in Figures 2–4. The crystal-
by 13C{1H} NMR spectroscopic studies, since after each indi-
vidual synthesis step the resonance signals for the newly in-
troduced organometallic fragments can be seen nicely. The
1H NMR spectra of 6, 12, and 15 reveal a singlet at about
3.10 (6, 15) and 2.94 ppm (12) corresponding to the acetyl-
enic protons that disappear upon coordination of the alkynyl
units to ruthenium(II) and rhenium(I). The aryl protons on
the 2-, 4-, and 6-positions of the central phenylene ring show
an upfield shift upon the coordination of the alkynyl groups
to ReI and RuII. Such a shift to a higher field in the C6H3
resonance signals in 10–12 compared with that in 6 and 15
may be suggestive of the electron richness of the respective
transition-metal building blocks {(h2-dppf)(h5-C5H5)Ru} and
N
{(tBu2bpy)Re(CO)3} leading to a reduced electron donation
from the alkynyl units. The 1H NMR spectrum of 30 also
confirms the successful formation of this compound, giving
two signals for the cyclopentadienyl bonded SiMe3 groups,
which arises from their unsymmetrical environment in the
final assembly. Furthermore, when compared to 29, the reso-
nance signal for the acetylene bonded SiMe3 entity under-
goes an upfield shift of 0.75 ppm, which can be explained by
the ring current of the chelating bipyridyl.
Figure 2. ORTEP drawing of 8. Thermal ellipsoids are shown at the 50%
probability level. The hydrogen atoms are omitted for clarity. Selected
The identity of the heterometallic complexes 10, 19, 21,
25, 28, and 30 were additionally evidenced from mass spec-
trometric investigations. The electrospray ionization mass
spectra (ESI-MS) of 10, 19, 21, 25, and 28 show ion peaks at
a mass-to-charge ratio (m/z) which correspond to [M+H]+.
For example, the ESI MS spectrum of heterohexametallic 30
is shown in Figure 1. It exhibits a prominent ion peak at
m/z=2524.7, which, according to the mass and isotope dis-
tribution pattern, is [30ꢀPF6]+, and confirms the elemental
composition and charge state. Further assigned peaks are at
m/z 2452.6 [30ꢀPF6ꢀSiMe3]+, 1262.9 [30ꢀPF6]2+, 749.1
ꢁ
ꢀ
ꢀ
bond lengths (Š) and angles (8): Ru1 P12.272(2), Ru1 P2 2.267(2),
ꢀ
ꢀ
ꢀ
ꢀ
Ru1 D3 1.885(1), Ru1 C40 2.009(9), C40 C41 1.198(11), C41 C42
ꢀ
ꢀ
ꢀ
1.455(12), C44 I1 2.102(13), Fe1 D11.637(4), Fe1 D2 1.643(4); P1-Ru1-
P2 96.90(8), Ru1-C40-C41 168.5(7), C40-C41-C42 174.9(8), C46-P3-C48
102.0(7), C46-P3-C54 102.9(8), C48-P3-C54 103.9(7) (D1=centroid of
ꢀ
ꢀ
ꢀ
C1 C5; D2=centroid of C6 C10; D3=centroid of C35 C39).
lographic data are given in Table 1. While complexes 8 and
26 crystallize in the monoclinic space group P21/n, com-
pound 12 is found in the monoclinic space group P21/a, and
[(C5H5)
(PPh3)2Ru(CO)]+,[25] and 579.2 [[Ti]
G
19 crystallizes in the triclinic space group P1. In the solid-
¯
A
state structure of 8, a part of the molecule is disordered and
has been refined to split occupancies of 0.50/0.50 (I1, P3 and
C43–C59). In the packing network, phenyl rings are found
close together, but due to the disorder (0.50/0.50) no inter-
molecular contact is present. There are two independent
molecules per asymmetric unit found in 12, of which only
X-ray crystallography: The solid-state structures of 8, 12, 19,
and 26 have been determined by single-crystal X-ray analy-
sis. Suitable crystals of 8, 12, 19, and 26 were obtained at
room temperature from diffusion of n-pentane into the re-
Chem. Eur. J. 2008, 14, 4948 – 4960
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
4953

H. Lang et al.
Table 1. Crystal and intensity collection data for 8, 12, and 19.
one is depicted in Figure 3. The
difference between these two
molecules is revealed by a dif-
ferent orientation of the alkynyl
ligand formed by rotation
around the acetylide unit.
8
12
19·4CH2Cl2
formula
Mr
C59H46FeIP3Ru
1131.69
C86H74N4O6P2Re2
1693.83
C96H87Cl10FeN2O3P3ReRhRu
2210.12
triclinic
crystal system
space group
a [Š]
b [Š]
c [Š]
monoclinic
P21/n
10.1173(3)
31.9585(7)
17.0011(4)
90
monoclinic
P21/a
22.4784(10)
11.5220(5)
29.1985(10)
90
¯
P1
14.2510(9)
18.6426(9)
19.0689(8)
97.161(4)
98.847(5)
109.849(5)
4622.4(4)
1.588
Complexes 8 and 19 contain
a
ACTHREUNG ACHTREUGN
{(h2-dppf)(h5-C5H5)Ru}–acet-
A
a [8]
b [8]
94.956(2)
90
5476.5(2)
1.373
99.824(3)
90
7451.4(5)
1.510
a
g [8]
rounding. The 1,1’-bis(diphenyl-
phosphino)ferrocene unit is in
an eclipsed geometry (8:
2.09(29)8; 19: 3.76(16)8), and
the cyclopentadienyl rings are
inclined at an angle of 6.56(49)8
(8) and 2.10(28)8 (19). Notable
is the dppf bite angle P-Ru-P
which is with 96.90(8)8 (8) and
98.59(8)8 (19) slightly smaller
than those ones found in
V [Š3]
1calcd [gcmꢀ3
]
F
N
2272
0.1”0.08”0.02
4
3384
0.7”0.4”0.1
4
2212
0.4”0.3”0.2
2
Z
m [mmꢀ1
]
1.227
3.346
2.186
V range [8]
index ranges
2.82 to 26.00
ꢀ12ꢂhꢂ12
ꢀ39ꢂkꢂ39
ꢀ20ꢂlꢂ20
50382
3.02 to 25.00
ꢀ26ꢂhꢂ26
ꢀ13ꢂkꢂ13
ꢀ34ꢂlꢂ34
48673
2.89 to 24.00
ꢀ16ꢂhꢂ16
ꢀ21ꢂkꢂ21
ꢀ21ꢂlꢂ21
30066
reflns collected
independent reflns
10712
12547
13556
0.0652
R
A
0.0947
0.0248
data/restraints/parameters
10712/443/748
1.033
0.0771/0.1948
0.1420/0.2249
2.222/ꢀ0.7812.629/
12547/0/901
1.148
0.0382/0.0845
0.0515/0.0875
ꢀ1.678
13556/0/1063
0.934
0.0509/0.1202
0.0902/0.1317
1.844/ꢀ1.564
[{(Ph3P)2
ide] complexes
101.17(7)8), but similar to relat-
N
A
GOF on F2
AHCTREUNG
R1[a]/wR2[a] [I^2s(I)]
R1[a]/wR2[a] (all data)
largest peak/hole [e Š
ꢀ3
ed
A
]
acet
ACHTREUNG
[a] R1=[ꢀ(jjFojꢀjFc jj)/jFo j); wR2=[ꢀ(w(F2oꢀF2c)2)/ꢀ(wFo4)]1/2. S=[ꢀw(Fo2ꢀFc2)2]/(nꢀp)1/2. n=number of re-
flections, p=parameters used.
Figure 4. ORTEP drawing of 19. Thermal ellipsoids are shown at the
50% probability level. The hydrogen atoms and four dichloromethane
molecules are omitted for clarity. Selected bond lengths (Š) and angles
ꢀ
ꢀ
ꢀ
ꢀ
(8): Re1 N12.810(6), Re1
N2 2.173(7), Re1 C9 1.919(10), Re1 C10
ꢀ
ꢀ
ꢀ
ꢀ
1.915(9), Re1 C11 1.960(10), Re1 C8 2.123(9), C7 C8 1.209(11), Ru1
ꢀ
ꢀ
ꢀ
Figure 3. ORTEP drawing of 12. Thermal ellipsoids are shown at the
50% probability level. The hydrogen atoms are omitted for clarity. Se-
P2 2.253(2), Ru1 P3 2.266(2), Ru1 D1 1.881(4), Ru1 C53 2.004(9),
C52 C53 1.213(11), Rh1 P12.334(2), Rh1 Cl12.406(2), Rh1 Cl2
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
lected bond lengths (Š) and angles (8): Re1 N12.518(5), Re1
N2
ꢀ
2.381(2), Rh1 D2 1.810(4), Fe1 D3 1.648(4), Fe1 D4 1.647(4); N1-Re1-
N2 75.2(2), Re1-C8-C7 176.5(7), C5-C7-C8 176.7(8), P2-Ru1-P3 98.59(8),
Ru1-C53-C52 175.7(7), C3-C52-C53 169.7(8), C1-P1-C30 104.1(4), C1-P1-
C36 105.9(4), C30-P1-C36 102.1(4), Cl1-Rh1-Cl2 93.23(8), Cl1-Rh1-P1
92.94(8), Cl2-Rh1-P1 87.56(8) (D1=centroid of C5H5; D2=centroid of
ꢀ
ꢀ
ꢀ
2.162(5), Re1 C19 1.903(7), Re1 C20 1.915(6), Re1 C21 1.954(7), C19
ꢀ
ꢀ
ꢀ
O1 1.149(7), C20 O2 1.152(7), C21 O3 1.144(8), Re1 C22 2.121(6),
ꢀ
ꢀ
C22 C23 1.212(9), C42 C43 1.182(10); N1-Re1-N2 73.92(18), Re1-C22-
C23 174.7(5), C22-C23-C24 179.7(8), C28-C42-C43 175.8(8), C26-P1-C30
102.7(3), C26-P1-C36 100.5(3), C30-P1-C36 101.8(3).
ꢀ
ꢀ
C5Me5; D3=centroid of C83 C87; D4=centroid of C88 C92).
4954
www.chemeurj.org
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2008, 14, 4948 – 4960

Mixed-Transition-Metal Acetylides
FULL PAPER
ꢁ
nium–phosphorus and ruthenium–carbon distances are as
expected and are in accordance with those found in related
complexes.[22,23] The ruthenium–s-acetylide unit is essentially
linear with angles between 168.5(7)8 and 175.7(7)8 and the
C CSiMe3)2}Cu)}C6H3][PF6] is the first example of a transi-
A
tion-metal system containing six different metals linked by
p-conjugated organic units. X-ray structure analyses show
the solid-state structure of four representative molecules.
ꢁ
distance of the C C bond is with 1.198(11) (8) and
1.213(11) Š (19) typical for terminal metal s-coordinated
carbon–carbon triple bonds.[22,23]
The structures of complexes 12 and 19 show a slightly dis-
torted octahedral geometry around Re1with three facial ar-
Experimental Section
General procedure: 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 over sodium/benzophenone ketyl; dichloromethane was purified by
distillation over calcium hydride. Amines were distilled over potassium
hydroxide. Celite (purified and annealed, Erg. B.6, Riedel de Haen) was
used for filtrations.
ꢀ ꢁ ꢀ
ranged carbonyl ligands. The Re C C C units are as ex-
pected essentially linear with bond angles of 174.7(5)–
ꢁ
179.7(8)8 and C C distances typical for metal–alkynyl sys-
tems.[6b,16] The Re1 C22 (2.121(6) Š) (12) and Re1 C8
(2.123(9) Š) (19) bonds are somewhat longer when com-
ꢀ
ꢀ
ꢀ
pared to the other Re CO separations (1.903(7)–
1.960(10) Š) and are indicative for little or no significant
metal-to-ligand p-back-bonding to the acetylide unit. Similar
Measurements: Infrared spectra were recorded with a Perkin Elmer
FTIR spectrometer Spectrum 1000. NMR spectra were recorded with a
Bruker Avance 250 spectrometer (1H NMR at 250.12 MHz and 13C{1H}
NMR at 62.86 MHz) in the Fourier transform mode. Chemical shifts are
reported in d units (parts per million) downfield from tetramethylsilane
ꢀ
Re C bond lengths are reported for related tricarbonyldi-
iminealkynylrhenium(I) complexes.[6b,16] In both compounds
1
(d=0.00 ppm) with the solvent as the reference signal (CDCl3: H NMR,
the N1-Re1-N2 bond angles (12, 73.92(18)8; 19, 75.2(2)8) are
less than 908, as required by the bite distance exerted by the
steric demand of the chelating bipyridine ligand.
d=7.26 ppm; 13C{1H} NMR, d=77.16 ppm).[31] 31P{1H} NMR spectra
were recorded at 101.255 MHz in CDCl3 with P(OMe)3 as an external
E
standard (d=139.0 ppm, relative to H3PO4 (85%) with d=0.00 ppm).
ESI-TOF mass spectra were recorded using a Mariner biospectrometry
workstation 4.0 (Applied Biosystems). Microanalyses were performed by
the Institute of Inorganic Chemistry and partly by the Institute of Organ-
ic Chemistry, Chemnitz, Technical University.
Coordination of the diphenylphosphino group to {RhCl2-
(h5-C5Me5)} in complex 19 results in a tetrahedral surround-
ed phosphorus atom, which in turn slightly increases the C-
P-C angles. The coordination sphere around the rhodium-
(III) ion shows noticeable deformations, which apparently
results from the steric demand of the phosphine building
block.
All other bond lengths and angles require no further dis-
cussion because they agree well with those parameters de-
scribed for related transition-metal complexes.[16,22,23,26]
The structure of the transmetallation product 26 in the
solid state was determined (Supporting Information). The
main structural feature is the distorted octahedral geometry
around Re1with three carbonyl ligands arranged in a facial
fashion as typical for ReI–tricarbonyl–diimine systems.[6b,16]
In the solid state, the molecules of complex 26 are involved
in p–p interactions, including all pyridine rings, and, hence,
2D layers along the crystallographic b and c axes are
formed (Supporting Information).
Materials: Trimethylsilylacetylene,[32] 1,3-diiodo-5-trimethylsilylethynyl
benzene (4),[5j] [(tBu2bpy)(CO)3ReCl] (17),[16b] [(tBu2bpy)(CO)3ReC CH]
C
ꢁ
(9),[33] [(h2-dppf)
A
benzene (13),[35] [(h5-C5Me5)RhCl2]2 (18),[36] [(Et2S)2PtCl2] (20),[37]
[(tht)AuCl] (22),[38] 5-ethynyl-2,2’-bipyridyl (23),[39] [(nbd)Mo(CO)4]
(27)[40] and [{[Ti](m-s,p-C CSiMe3)2}Cu
G
N
ꢁ
ꢁ
pared according to published procedures. All other chemicals were pur-
chased from commercial suppliers and were used as received.
Preparation of 1-trimethylsilylethynyl-3-iodo-5-diphenylphosphinoben-
zene (5): n-Butyllithium (2.20 mL, 1.6m in n-hexane, 3.52 mmol) was
slowly added to a solution of compound 4 (1.50 g 3.52 mmol) in diethyl
ether (60 mL) at ꢀ808C. The reaction mixture was stirred for 60 min at
this temperature. Then chlorodiphenylphosphine (0.90 g, 4.08 mmol) was
slowly added with a syringe and stirring was continued for 10 min at
ꢀ808C. After warming the reaction solution to room temperature over
30 min with stirring, it was filtered through a pad of Celite and all vola-
tile materials were removed from the filtrate to give a clear viscous oil
which was purified by column chromatography on silica gel. Complex 5
was eluted with petroleum ether/diethyl ether (10:1 v/v). After removal
of the solvents using an oil-pump vacuum, a colorless solid remained.
1
Yield: 1.38 g (2.85 mmol, 81%); m.p. 1248C; H NMR (250 MHz, CDCl3,
258C): d=0.22 (s, 9H; SiMe3), 7.27–7.40 (m, 10H (C6H5) + 1 H (CH3)),
6
Conclusion
7.50 (dpseudo-t, JHP =6.4 Hz, JHH =1.5 Hz, 1H; C6H3), 7.79 ppm (pseudo-
t, JHH =1.5 Hz, 1H; C6H3); 13C{1H} NMR (62.9 MHz, CDCl3, 258C): d=
This report describes the synthesis of a series of heteromul-
timetallic complexes featuring two, three, four, five, or even
six different transition metals, including titanium, molybde-
num, rhenium, iron, ruthenium, rhodium, copper, and gold,
which are connected by carbon-rich organic bridging units
ꢁ
ꢁ
ꢀ0.1(Si Me3), 94.5 (d, JCP =6.2 Hz, Ci/C6H3), 96.6 (C C), 103.0 (C C),
125.4 (d, JCP =4.3 Hz, Ci/C6H3), 128.9 (d, JCP =7.2 Hz, CH/C6H5), 129.3
(CH/C6H5), 134.0 (d, JCP =20.1Hz, CH/C6H5), 136.0 (d, JCP =21.4 Hz,
CH/C6H3), 136.0 (d, JCP =11 Hz, Ci/C6H5), 140.8 (CH/C6H3), 140.8 (d,
J
CP =17.8 Hz, Ci/C6H3), 141.9 ppm (d, JCP =18.9 Hz, CH/C6H3); 31P{1H}
NMR (101.25 MHz, CDCl3, 258C): d=ꢀ5.5 ppm (s, PPh2); IR (KBr): n˜ =
2163 cmꢀ1 (m, C C); elemental analysis calcd (%) for C23H22IPSi
based on the 1,3-bis(ethynyl)-5-diphenylphosphinobenzene
G
ꢁ
(484.39): C 57.03, H 4.58; found: C 57.43, H 4.87.
core. The consecutive synthesis procedure allowed the
straightforward preparation of a series of such complexes
that should enable us to systematically develop the field of
heteromultimetallic molecules, which is up to now only
Preparation of 1-ethynyl-3-iodo-5-diphenylphosphinobenzene (6):
[nBu4N]F (1m in THF, 1.70 mL, 1.70 mmol) was added to a solution of
compound 5 (0.75 g, 1.55 mmol) in THF (30 mL). The dark solution was
stirred for 1h at 25 8C and afterwards the solvent was removed under re-
duced pressure. The residue was purified by column chromatography on
alumina using a mixture of petroleum ether/diethyl ether (2:1, v/v) as
5
rarely investigated. Complex [1-{(h2-dppf)
A
ꢁ
ꢁ
ꢁ
3-{(tBu2bpy)(CO)3ReC C}-5-{PPh2-AuC C-bpy({[Ti](m-s,p-
Chem. Eur. J. 2008, 14, 4948 – 4960
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
4955

H. Lang et al.
eluent. After removing all volatiles under reduced pressure, compound 6
was obtained as a colorless solid. Yield: 0.49 g (1.19 mmol, 77%); m.p.
1368C; 1H NMR (250 MHz, CDCl3, 258C): d=3.08 (s, 1H; =CH), 7.27–
matography on silica gel using a mixture of diethyl ether/petroleum ether
(1:1, v/v) as eluent. After removal of all volatile materials under reduced
pressure compound 15 could be isolated as a colorless solid. Yield:
320 mg (1.031 mmol, 69%).
7.40 (m, 10H (C5H6) + 1 H (CH3)), 7.58 (dpseudo-t, JHP =6.6 Hz, JHH
=
6
1.5 Hz, 1H; C6H3), 7.80 ppm (pseudo-t, JHH =1.5 Hz, 1H; C6H3); 13C{1H}
Data for 15: M.p. 1438C; 1H NMR (250 MHz, CDCl3, 258C): d=3.08 (s,
ꢁ
ꢁ
NMR (62.9 MHz, CDCl3, 258C): d=79.1(C CH), 81.8 (C CH), 94.5 (d,
CP =6.5 Hz, Ci/C6H3), 124.4 (d, JCP =6.7 Hz, Ci/C6H3), 128.9 (d, JCP
2H; =CH), 7.30–7.42 (m, 10H; C6H5), 7.45 (dd, JHP =7.1Hz, JHH
=
1.6 Hz, 2H; C6H3), 7.63 ppm (t, JHH =1.6 Hz, 1H; C6H3); 13C{1H} NMR
J
=
7.2 Hz, CH/C6H5), 129.4 (CH/C6H5), 133.9 (d, JCP =20 Hz, CH/C6H5),
135.8 (d, JCP =11 Hz, Ci/C6H5), 136.1 (d, JCP =19.2 Hz, CH/C6H3), 140.8
(CH/C6H3), 141.1 (d, JCP =18.1 Hz, Ci/C6H3), 142.3 ppm (d, JCP =20.8 Hz,
CH/C6H3); 31P{1H} NMR (101.25 MHz, CDCl3, 258C): d=ꢀ5.7 ppm (s,
ꢁ
ꢁ
(62.9 MHz, CDCl3, 258C): d=78.7 (C CH), 82.4 (C CH), 122.8 (d, JCP
=
7.4 Hz, Ci/C6H3), 128.8 (d, JCP =7.2 Hz, CH/C6H5), 129.3 (CH/C6H5),
133.9 (d, JCP =20 Hz, CH/C6H5), 135.8 (CH/C6H3), 136.0 (d, JCP =10.8 Hz,
Ci/C6H5), 137.1 (d, JCP =19.8 Hz, CH/C6H3), 139.0 ppm (d, JCP =15.5 Hz,
Ci/C6H3); 31P{1H} NMR (101.25 MHz, CDCl3, 258C): d=ꢀ6.4 ppm (s,
PPh2); IR (KBr): n˜ =3288 cmꢀ1 (s, C H); elemental analysis calcd (%)
ꢁ ꢀ
for C20H14IP (412.2): C 58.28, H 3.42; found: C 58.81, H 3.56.
ꢁ ꢀ
PPh2); IR (KBr): n˜ =3289 (s, C H); elemental analysis calcd (%) for
C22H15P (310.33): C 85.15, H 4.87; found: C 84.80, H 5.02.
Preparation of 1,3-bis(trimethylsilylethynyl)-5-diphenylphosphinoben-
zene (14): Trimethylsilylacetylene (0.75 g, 7.65 mmol), [(PPh3)2PdCl2]
(80 mg), and CuI (40 mg) were added To compound 13 (0.80 g,
1.90 mmol) dissolved in degassed diisopropylamine (40 mL). The result-
ing reaction mixture was heated to 508C and stirred 48 h. After cooling
to 258C, the reaction mixture was filtered through a pad of Celite and all
volatiles were removed under reduced pressure. The remaining material
was subjected to column chromatography on silica gel using a mixture of
petroleum ether/diethyl ether (5:1, v/v) as eluent. Compound 14 was iso-
lated as a colorless solid after evaporation of all volatile materials under
reduced pressure. Yield: 650 mg (1.430 mmol, 75%); m.p. 1328C;
1H NMR (250 MHz, CDCl3, 258C): d=0.25 (s, 18H; SiMe3), 7.30–7.40
5
Preparation of [1-{(h2-dppf)
(h -C5H5)RuC C}-3-I-5-(PPh2)C6H3] (8):
ꢁ
Complex [(h2-dppf)
(h5-C5H5)RuCl] (200 mg, 0.265 mmol) was heated to
reflux in methanol (30 mL) for 20 min to give a yellow orange suspension
to which a single portion of 6 (130 mg, 0.315 mmol) was added. The reac-
tion mixture was then refluxed for 30 min. During that time it became a
clear orange-red solution, which afterwards was cooled to room tempera-
ture. Addition of two equivalents (10 mg) of sodium resulted in the rapid
precipitation of a yellow solid. Stirring was continued for 1h, and then
all volatile materials were removed under reduced pressure. The residue
was filtered through a pad of Celite using dichloromethane as solvent.
The solvent was removed, and the remaining material was purified by
column chromatography on silica gel using a mixture of petroleum ether/
THF (4:1, v/v) as eluent. After removal of all volatiles under reduced
pressure, compound 8 could be isolated as a yellow solid. Yield: 230 mg
(0.203 mmol, 76%); 1H NMR (250 MHz, CDCl3, 258C): d=3.98
(dpseudo-t, JHP =1.2 Hz, JHH =2.4 Hz, 2H; C5H4), 4.10 (brs, 2H; C5H4),
4.29 (s, 5H; C5H5), 4.30 (brs, 2H; C5H4), 5.12 (brs, 2H; C5H4), 7.14–7.57
(m, 26H (C6H5) + 3H (C6H3))), 7.72–7.81ppm (m, 4H; C 6H5); 13C{1H}
NMR (62.9 MHz, CDCl3, 258C): d=68.2 (pseudo-t, JCP =2.4 Hz, CH/
(m, 10H; C6H5), 7.41(dd,
JHP =7 Hz, JHH =1.6 Hz, 2H; C6H3), 7.62 ppm
(t, JHH =1.6 Hz, 1H; C6H3); 13C{1H} NMR (62.9 MHz, CDCl3, 258C): d=
ꢁ
ꢁ
0.0 (SiMe3), 95.7 (C C), 103.9 (C C), 123.8 (d, JCP =7.7 Hz, Ci/C6H3),
128.8 (d, JCP =7 Hz, CH/C6H5), 129.1 (CH/C6H5), 133.9 (d, JCP =19.8 Hz,
CH/C6H5), 135.9 (CH/C6H3), 136.2 (d, JCP =10.9 Hz, Ci/C6H5), 136.6 (d,
J
CP =20.2 Hz, CH/C6H3), 138.5 ppm (d, JCP =15.2 Hz, Ci/C6H3); 31P{1H}
NMR (101.25 MHz, CDCl3, 258C): d=ꢀ6.2 ppm (s, PPh2); IR (KBr): n˜ =
2161 cmꢀ1 (m, C C); elemental analysis calcd (%) for C28H31PSi2
ꢁ
(454.70): C 73.96, H 6.87; found: C 73.82, H 6.78.
C5H4), 71.4 (pseudo-t,
2.0 Hz, CH/C5H4), 76.6 (pseudo-t, JCP =4.8 Hz, CH/C5H4), 84.9 (pseudo-t,
CP =2.4 Hz, C5H5), 88.4 (pseudo-t, JCP =24.3 Hz, Ci/C5H4), 95.1(d, JCP
JCP =2.8 Hz, CH/C5H4), 73.2 (pseudo-t, JCP =
ꢁ ꢀ
Preparation of 1,3-(C
(16): 2-Methyl-3-butyn-2-ol (0.64 g, 7.61mmol),
C
C
ACHTREUNG
ACHTREUNG
J
=
and CuI (40 mg) were added to compound 13 (0.80 g, 1.90 mmol) dis-
solved in degassed diisopropylamine (50 mL) . The resulting reaction
mixture was refluxed for 20 h. After cooling to 258C, it was filtered
through a pad of Celite, and all volatiles were removed under reduced
pressure. The remaining material was purified by column chromatogra-
phy on silica gel using a mixture of petroleum ether/diethyl ether (1:5, v/
v) as eluent. After removing all solvents under reduced pressure, com-
pound 16 was obtained as a colorless solid. Yield: 690 mg (1.618 mmol,
85%); m.p. 1338C; 1H NMR (250 MHz, CDCl3, 258C): d=1.55 (s, 12H;
CH3), 2.44 (brs, 2H; OH), 7.24–7.38 (m, 10H (C6H5) + 2H (C6H3)),
7.45 ppm (t, JHH =1.6 Hz, 1H; C6H3); 13C{1H} NMR (62.9 MHz, CDCl3,
ꢁ
ꢁ
8.8 Hz, C-I/C6H3), 111.4 (RuC C), 124.8 (t, JCP =25.0 Hz, RuC C), 127.2
(pseudo-t, JCP =4.8 Hz, CH/C6H5(dppf)), 127.4 (pseudo-t, JCP =4.8 Hz,
CH/C6H5(dppf)), 128.6 (d, CP =7.0 Hz, CH/C6H5), 128.8 (CH/C6H5-
(dppf)), 128.9 (CH/C6H5), 129.2 (CH/C6H5(dppf)), 132.4 (d, JCP =6.3 Hz,
Ci/C6H3), 133.8 (pseudo-t, JCP =5.7 Hz, CH/C6H5(dppf)), 133.9 (d, JCP
19.8 Hz, CH/C6H5), 134.2 (pseudo-t, JCP =5.7 Hz, CH/C6H5(dppf)), 134.9
(d, JCP =16.8 Hz, CH/C6H3), 136.8 (d, JCP =23.0 Hz, CH/C6H3), 137.2 (d,
CP =11.0 Hz, Ci/C6H5), 139.1 (d, JCP =14.5 Hz, Ci/C6H3), 140.1 (CH/
C6H3), 140.8 (pseudo-t, JCP =23.0 Hz, Ci/C6H5(dppf)), 141.9 ppm (pseudo-
AHCTREUNG
A
J
A
ACHTREUNG
G
=
AHCTREUNG
J
AHCTREUNG
t,
J
CP =22.8 Hz, Ci/C6H5
(dppf); 31P{1H} NMR (101.25 MHz, CDCl3,
A
258C): d=ꢀ5.1(s, PPh2), 53.7 ppm (s, dppf); IR (KBr): n˜ =2055 cmꢀ1 (m,
ꢁ
ꢁ
258C): d=31.5 (CH3), 65.6 (C-OH), 81.1 (C C), 95.1(C C), 123.4 (d,
CP =7.7 Hz, Ci/C6H3), 128.8 (d, JCP =6.8 Hz, CH/C6H5), 129.2 (CH/C6H5),
ꢁ
nC CRu); elemental analysis calcd (%) for C59H46FeIP3Ru (1131.75): C
J
62.62, H 4.10; found: C 62.62, H 4.49.
133.9 (d, JCP =19.6 Hz, CH/C6H5), 135.2 (CH/C6H3), 136.07 (d, JCP
19.1 Hz, CH/C6H3), 136.13 (d, JCP =11.1 Hz, Ci/C6H5), 138.5 ppm (d, JCP
=
ꢁ
ꢁ
Preparation of [1-(Me3SiC C)-3-{(tBu2bpy)(CO)3ReC C}-5-(PPh2)C6H3]
(11): [(PPh3)2PdCl2] (8 mg) and CuI (4 mg) were added to 9 (130 mg,
0.231mmol) and 5 (120 mg, 0.248 mmol) dissolved in degassed triethyl-
A
=
14.9 Hz, Ci/C6H3); 31P{1H} NMR (101.25 MHz, CDCl3, 258C): d=
ꢀ6.3 ppm (s, PPh2); IR (KBr): n˜ =3341cm ꢀ1 (s, O H); elemental analysis
ꢀ
amine (30 mL). The resulting reaction mixture was heated to reflux over-
calcd (%) for C28H27O2P (426.49): C 78.85, H 6.38; found: C 78.38, H
6.74.
night. After cooling to 258C, all volatiles were removed using an oil-
pump vacuum, and the remaining residue was subjected to column chro-
matography on silica gel using a mixture of diethyl ether/n-hexane (1:1,
v/v) as eluent. Complex 11 was obtained as a yellow solid. Yield: 70 mg
(0.076 mmol, 33% based on 9); 1H NMR (250 MHz, CDCl3, 258C): d=
0.15 (s, 9H; SiMe3), 1.45 (s, 18H; tBu), 6.90–7.03 (m, 3H; C6H3), 7.14–
7.30 (m, 10H; C6H5), 7.44 (dd, JH5H6 =6 Hz, JH5H3 =1.9 Hz, H5/tBu2bpy),
Preparation of 1,3-bis(ethynyl)-5-diphenylphosphinobenzene (15)
G
Preparation from 14: [nBu4N]F (1.0m in THF, 1.5 mL, 1.50 mmol) was
slowly added to a solution of 14 (600 mg, 1.32 mmol) in THF (30 mL).
The resulting reaction solution was stirred for 1h at 25 8C. Afterwards all
volatiles were removed under reduced pressure, and the remaining mate-
rial was purified by column chromatography on silica gel. Eluting with a
mixture of diethyl ether/petroleum ether (1:1, v/v) gave compound 15 as
a colorless solid. Yield: 360 mg (1.160 mmol, 88%).
8.07 (d,
JH3H5 =1.9 Hz, H3/tBu2bpy), 8.94 ppm (d, JH6H5 =6 Hz, H6/
tBu2bpy); 31P{1H} NMR (101.25 MHz, CDCl3, 258C): d=ꢀ6.0 ppm (s,
PPh2); IR (KBr): n˜ =1900, 2004 (s, CO), 2088 cmꢀ1 (w,
ꢁ
ꢁ
C CRe), 2156 (w, C CSi); elemental analysis calcd (%) for
C46H46N2O3PReSi (920.15): C 60.04, H 5.04, N 3.04; found: C 59.67, H
5.15, N 2.89.
Preparation from 16: KOH (420 mg, 7.50 mmol) was added to 16
(640 mg 1.50 mmol) dissolved in toluene (30 mL), and the resulting reac-
tion mixture was heated to 808C for 5 h. After cooling to 258C it was fil-
tered through a pad of Celite and all volatiles were removed under re-
duced pressure. The remaining orange oil was subjected to column chro-
ꢁ
ꢁ
Preparation of [1-(HC C)-3-{(tBu2bpy)(CO)3ReC C}-5-(PPh2)C6H3]
(12)
4956
www.chemeurj.org
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2008, 14, 4948 – 4960

Mixed-Transition-Metal Acetylides
FULL PAPER
Preparation from 11: [nBu4N]F (1.0m in THF, 0.1mL, 0.10 mmol) was
added to a solution of 11 (60 mg 0.065 mmol) in THF (15 mL). After 1 h
of stirring at 258C, all volatiles were removed under vacuum, and the re-
sidual material was purified by column chromatography on silica gel
using a mixture of diethyl ether/n-hexane (2:1, v/v) as eluent. Complex
12 was obtained as a yellow solid. Yield: 45 mg (0.053 mmol, 82%).
J
HP =7.1Hz,
J
HH =1.6 Hz, 1H; C6H3), 7.10–7.52 (m, 26H (C6H5) + 1H
(C6H3)), 7.42 (dd, 3JH5H6 =5.8 Hz, 4JH5H3 =1.9 Hz, 2H; H5/tBu2bpy), 7.65–
7.74 (m, 4H; C6H5), 8.06 (d, 4JH3H5 =1.9 Hz, 2H; H3/tBu2bpy), 8.98 ppm
(d, 3JH6H5 =5.8 Hz, 2H; H6/tBu2bpy); 13C{1H} NMR (62.9 MHz, CDCl3,
258C): d=30.5 (CH3), 35.6 (C
C5H4), 71.5 (pseudo-t, CP =2.8 Hz, CH/C5H4), 72.9 (pseudo-t, JCP
2.0 Hz, CH/C5H4), 76.9 (pseudo-t, JCP =4.8 Hz, CH/C5H4), 84.7 (pseudo-t,
A
J
=
Preparation from 15: LiN(SiMe3)2 (160 mg, 0.956 mmol) was added to a
A
J
CP =2.4 Hz, C5H5), 88.5 (pseudo-t,
J
CP =24.3 Hz, Ci/C5H4), 105.7
cooled (08C) solution of (15) (300 mg, 0.967 mmol) in toluene (50 mL).
The resulting reaction mixture was stirred for 3 h at 08C. Afterwards 17
(200 mg, 0.348 mmol) was added, and the reaction mixture was refluxed
for 5 h. After cooling to room temperature, the toluene was removed by
rotary evaporation, and the residue was subjected to column chromatog-
raphy on silica gel. A diethyl ether/n-hexane mixture of ratio 2:1(v/v)
ꢁ
ꢁ
ꢁ
A
tBu2bpy), 124.1 (CH/tBu2bpy), 125.2–129.2 (C6H5 + C6H3), 132.2–135.0
(C6H5 + C6H3), 138.1 (d, JCP =11.1 Hz, Ci/C6H5), 140.8 (pseudo-t, JCP
21.0 Hz, Ci/C6H5(dppf)), 142.3 (pseudo-t, JCP =22.8 Hz, Ci/C6H5(dppf),
=
A
ACHTREUNG
153.0 (CH/tBu2bpy), 155.8 (Ci/tBu2bpy), 162.7 (Ci/tBu2bpy), 193.1 (CO),
198.6 ppm(CO); 31P{1H} NMR (101.25 MHz, CDCl3, 258C): d=ꢀ5.3 (s,
was used as eluent, eluting first the excess of 1,3-bis
A
PPh2), 53.7 ppm (s, dppf); IR (KBr): n˜ =1892, 1901, 2003 (s, CO),
phosphinobenzene followed by compound 12 and finally unreacted 17.
2065 cmꢀ1 (m, C CRu); MS (ESI-TOF): m/z: 1568.9 [M+H] , 749.3
+
ꢁ
Complex 12 was obtained as
a yellow powder. Yield: 140 mg
[(C5H5)
(dppf)Ru(CO)]+;
elemental
analysis
calcd
(%)
for
(0.165 mmol, 47% based on 17). 1H NMR (250 MHz, CDCl3, 258C): d=
1.45 (s, 18H; tBu), 2.94 (s, 1H; CH), 6.93 (dpseudo-t, 3JHP =6.5 Hz,
ꢁ
C82H70FeN2O3P3ReRu (1567.51): C 62.83, H 4.50, N 1.79; found: C 63.33,
H 4.91, N 1.50.
4JHH =1.6 Hz, 1H; C6H3), 6.95 (pseudo-t, 4JHH =1.6 Hz, 1H; C6H3), 7.07
(dpseudo-t, 3JHP =9 Hz, JHH =1.6 Hz, 1H; C6H3), 7.16–7.31 (m, 10H;
5
[1-{(h2-dppf)
(h -C5H5)RuC C}-3-{(tBu2bpy)(CO)3
ꢁ
Preparation
ReC C}-5-{PPh2Rh
of
3
4
(h5-C5Me5)Cl2}C6H3] (19): Complex (10) (80 mg,
C6H5), 7.44 (dd, JH5H6 =5.8 Hz, JH5H3 =1.9 Hz, 2H; H5/tBu2bpy), 8.08 (d,
H3H5 =1.9 Hz, 2H; H3/tBu2bpy), 8.95 ppm (d, JH6H5 =5.8 Hz, 2H; H6/
tBu2bpy); 13C{1H} NMR (62.9 MHz, CDCl3, 258C): d=30.5 (CH3), 35.6
ꢁ
J
0.051mmol) was dissolved in dichloromethane (10 mL) and was then
added dropwise to 18 (15 mg, 0.024 mmol) dissolved in dichloromethane
(10 mL). The resulting red solution was stirred for 1 h at 258C. After-
wards, the solvent was reduced in volume to about 3 mL and compound
19 was precipitated by addition of n-hexane (20 mL) and washed with n-
hexane (2”15 mL) to give an orange red solid. Yield: 78 mg
ꢁ
ꢁ
ꢁ
(C
tBu2bpy), 121.6 (d, JCP =6.8 Hz, Ci/C6H3), 124.2 (CH/tBu2bpy), 128.3 (d,
CP =9.5 Hz, Ci/C6H3), 128.6 (d, JCP =7 Hz, CH/C6H5), 128.8 (CH/C6H5),
A
J
133.1 (d, JCP =15.8 Hz, CH/C6H3), 133.8 (d, JCP =19.6 Hz, CH/C6H5),
136.1 (CH/C6H3), 136.6 (d, JCP =9.5 Hz, Ci/C6H5), 136.8 (d, JCP =12.4 Hz,
Ci/C6H3), 137.3 (d, JCP =24.9 Hz, CH/C6H3), 152.9 (CH/tBu2bpy), 155.8
(Ci/tBu2bpy), 162.9 (Ci/tBu2bpy), 192.9 (CO), 198.3 ppm (CO); 31P{1H}
1
(0.042 mmol, 86% based on 18).; H NMR (250 MHz, CDCl3, 258C): d=
1.34 (d, JHRh =3.4 Hz, 15H; C5Me5), 1.42 (s, 18H; tBu), 3.89 (brs, C5H4),
4
3.93 (brs, C5H4), 4.22 (s, C5H5), 4.23 (brs, C5H4), 5.03 (brs, C5H4), 6.99
(dpseudo-t, JHP =9.5 Hz, JHH =1.5 Hz, 1H; C6H3), 7.05–7.56 (m, 22H
(C6H5) + 2H (H5/tBu2bpy) + 2H (C6H3)), 7.64–7.80 (m, 8H; C6H5),
8.06 (d, JHH =1.6 Hz, 2H; H3/tBu2bpy), 8.99 ppm (d, JHH =6 Hz, 2H; H6/
NMR (101.25 MHz, CDCl3, 258C): d=ꢀ6.3 ppm (s, PPh2); IR (KBr): n˜ =
ꢀ1
ꢁ
ꢁ ꢀ
1884, 1901, 2004 (s, CO), 2092 (w, C CRe), 3299 cm (m, C H); ele-
mental analysis calcd (%) for C43H38N2O3PRe (847.97): C 60.91, H 4.52,
N 3.30; found: C 60.76, H 4.84, N 3.18.
tBu2bpy); 31P{1H} NMR (101.25 MHz, CDCl3, 258C): d=29.8 (d, JPRh
=
5
ꢁ
Preparation
of
[1-{(h2-dppf)
(h -C5H5)RuC C}-3-{(tBu2bpy)(CO)3
144 Hz, RhPPh2), 53.9 ppm (s, dppf); IR (KBr): n˜ =1896, 2003 (s, CO),
2063 cmꢀ1 (m, C CRu); MS (ESI-TOF): m/z: 1877.9 [M+H] , 749.2
+
ꢁ
ReC C}-5-(PPh2)C6H3] (10)
ꢁ
[(C5H5)
(dppf)Ru(CO)]+;
elemental
analysis
calcd
(%)
for
Preparation from 8: [(PPh3)2PdCl2] (5 mg) and CuI (3 mg) were added to
8 (150 mg, 0.133 mmol) and 9 (75 mg, 0.133 mmol) dissolved in a de-
gassed mixture of THF (10 mL) and triethylamine (20 mL). The reaction
mixture was heated to reflux for 8 h. Afterwards all volatiles were re-
moved using an oil pump vacuum, and the residual material was subject-
ed to column chromatography over alumina. Using diethyl ether as
eluent gave first unreacted starting materials, followed by the homo-cou-
pled product, and finally an orange red band from which complex 10
could be isolated as an orange solid. Yield: 35 mg (0.022 mmol, 17%).
C92H85Cl2FeN2O3P3ReRhRu (1876.55): C 58.89, H 4.56, N 1.49; found: C
58.99, H 4.68, N 1.40.
Preparation of trans-[{1-[(h2-dppf)
ReC C]-5-(PPh2)C6H3}2PtCl2] (21):
0.027 mmol) in dichloromethane (20 mL) was treated with 10 (90 mg,
0.057 mmol) and stirred for 2 h at 258C. Subsequently, the solvent was re-
duced in volume to 3 mL and addition of n-hexane (20 mL) caused the
precipitation of complex 21, which was washed with n-hexane (2”10 mL)
and dried using an oil pump vacuum. Yield: 70 mg (0.021mmol, 76%
based on 20); 1H NMR (250 MHz, CDCl3, 258C): d=1.35 (s, 36H; tBu),
3.87 (brs, 4H; C5H4), 3.96 (brs, 4H; C5H4), 4.16 (brs, 4H; C5H4), 4.19 (s,
5
ꢁ
A
ꢁ
Preparation from 12—method A: [NH4]PF6 (20 mg, 0.12 mmol) were
added to 7 (80 mg, 0.11 mmol) and 12 (100 mg, 0.12 mmol) dissolved in
dichloromethane and methanol (30 mL, ratio 1:1) . The reaction solution
was stirred for 5 h at 258C, followed by the addition of DBU (25 mg,
0.164 mmol). Stirring was continued for 1 h. Then all volatiles were re-
moved using an oil pump vacuum, and the residue was purified by
column chromatography on silica gel. Excess 12 was removed with tolu-
ene/dichloromethane (10:1, v/v) and compound 10 was eluted with tolu-
ene/THF (20:1, v/v). After precipitation from a concentrated solution in
dichloromethane by the addition of n-hexane, complex 10 was isolated as
an orange solid. Yield: 70 mg (0.045 mmol, 41% based on 7).
10H; C H5), 5.17 (brs, 4H; C5H4), 6.76–6.85 (m, 2H; C6H3), 7.04–7.51
(m, 4H (C6H3) + 4H (H5/tBu2bpy) + 40H (C6H5)), 7.59–7.75 (m, 20H;
5
C6H5), 8.01(d,
JH3H5 =1.7 Hz, 4H; H3/tBu2bpy), 8.90 ppm (d, JH6H5 =
5.8 Hz, 4H; H6/tBu2bpy); 31P{1H} NMR (101.25 MHz, CDCl3, 258C): d=
19.1 (s, JPPt =2643 Hz, PtPPh2), 53.8 ppm (s, dppf); IR (KBr): n˜ =1892,
1903, 2003 (s, CO), 2062 cmꢀ1 (m, C CRu); MS (ESI-TOF): m/z: 3401.5
ꢁ
[M+H]+, 749.1[(C 5H5)
A
for C164H140Cl2Fe2N4O6P6PtRe2Ru2 (3401.0): C 57.92, H 4.15, N 1.65;
found: C 57.76, H 4.20, N 1.50.
Preparation from 12—method B: [NH4]PF6 (20 mg, 0.12 mmol) and
KOtBu (15 mg, 0.13 mmol) were simultaneously added to 7 (80 mg,
0.11 mmol) and 12 (100 mg, 0.12 mmol) dissolved in dichloromethane/
methanol (1:1, 30 mL). The resulting solution was stirred for 4 h at 25 8C
5
[1-{(h2-dppf)
(h -C5H5)RuC C}-3-{(tBu2bpy)(CO)3
ꢁ
Preparation
of
ꢁ
ꢁ
ReC C}-5-(PPh2AuC C-bpy)C6H3] (25): Compound 23 (15 mg,
0.083 mmol) and CuI (1mg) were added to 22 (20 mg, 0.063 mmol) dis-
solved in THF (10 mL) and diethylamine (10 mL). The solution was
stirred at 258C for 30 min. The resulting turbid reaction mixture was fil-
tered using a cannula into a stirred solution of 10 (105 mg, 0.067 mmol)
in THF (10 mL) and stirred for 1 h. After removal of all volatiles, the re-
maining residue was subjected to column chromatography on silica gel.
As eluent a mixture of toluene/THF (20:1, v/v) was used. The first
orange band contained unreacted 10 and the second band yielded com-
plex 25 as a yellow solid. Yield: 75 mg (0.039 mmol, 62% based on 22);
until compound
7 was completely consumed, which was proven by
31P{1H} NMR spectroscopy. Subsequently, all volatiles were removed
under reduced pressure. The workup method was identical to that de-
scribed above. Yield: 110 mg (0.070 mmol, 66% based on 7).
Data for 10: 1H NMR (250 MHz, CDCl3, 258C): d=1.42 (s, 18H; tBu),
3.90 (dpseudo-t, JHP =1.3 Hz, JHH =2.4 Hz, 2H; C5H4), 3.98 (brs, 2H;
C5H4), 4.20 (s, 5H; C5H5), 4.22 (brs, 2H; C5H4), 5.12 (brs, 2H; C5H4),
6.74 (dpseudo-t, JHP =10.7 Hz, JHH =1.6 Hz, 1H; C6H3), 6.80 (dpseudo-t,
Chem. Eur. J. 2008, 14, 4948 – 4960
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
4957

H. Lang et al.
1H NMR (250 MHz, CDCl3, 258C): d=1.43 (s, 18H; tBu), 3.92 (dpseudo-
t, JHP =1.1 Hz, JHH =2.4 Hz, 2H; C5H4), 4.03 (brs, 2H; C5H4), 4.22 (s,
5H; C5H5), 4.24 (brs, 2H; C5H4), 5.02 (brs, 2H; C5H4), 6.78 (dpseudo-t,
31P{1H} NMR (101.25 MHz, CDCl3, 258C): d=ꢀ145.1 (septet, JPF
=
713 Hz, PF6), 40.8 (AuPPh2), 53.7 ppm (dppf); IR (KBr): n˜ =1893, 1904,
ꢀ1
ꢁ
ꢁ
2003 (s, CO), 2060 (m, C CRu), 2117 cm (w, C CAu); MS (ESI-TOF):
m/z: 2524.7 [MꢀPF6]+, 2452.6 [MꢀPF6ꢀSiMe3]+, 1262.9 [MꢀPF6]2+
,
J
J
HP =11.8 Hz, JHH =1.6 Hz, 1H; C6H3), 6.96 (dpseudo-t, JHP =15.8 Hz,
HH =1.6 Hz, 1H; C6H3), 7.07–7.52 (m, 26H (C6H5) + 1 H (H5’/bpy) +
749.1[(C 5H5)
(dppf)Ru(CO)]+; elemental analysis calcd (%) for
G
C120H121AuCuF6FeN4O3P4ReRuSi4Ti (2669.03): C 54.00, H 4.57, N 2.10;
found: C 54.76, H 4.80, N 2.04.
2H (H5/tBu2bpy) + 1 H (CH3)), 7.63–7.74 (m, 4H; C6H5), 7.80 (ddd,
6
3JH4’H3’ =7.8 Hz, 3JH4’H5’ =7.8 Hz, 4JH4’H6’ =1.8 Hz, 1H; H4’/bpy), 7.87 (dd,
3JH4H3 =8.2 Hz, 4JH4H6 =2.2 Hz, 1H; H4/bpy), 8.30 (dd, 3JH3H4 =8.2 Hz,
5JH3H6 =0.8 Hz, 1H; H3/bpy), 8.37 (ddd, 3JH3’H4’ =7.8 Hz, 4JH3’H5’ =1.0 Hz,
5JH3’H6’ =1.0 Hz, 1H; H3’/bpy), 8.42 (d, 4JH3H5 =1.7 Hz, 2H; H3/tBu2bpy),
8.66 (ddd, 3JH6’H5’ =4.9 Hz, 4JH6’H4’ =1.8 Hz, 5JH6’H3’ =1.0 Hz, 1H; H6’/bpy),
8.79 (dd, 4JH6H4 =2.2 Hz, 5JH6H3 =0.8 Hz, 1H; H6/bpy), 8.97 ppm (d,
3JH6H5 =6.0 Hz, 2H; H6/tBu2bpy); 31P{1H} NMR (101.25 MHz, CDCl3,
258C): d=41.2 (s, AuPPh2), 53.8 ppm (s, dppf); IR (KBr): n˜ =1895, 1904,
X-ray data collection and structure determinations of 8, 12, 19, and 26:
Crystal data for 8, 12, and 19 are summarized in Table 1(for 26 see Sup-
porting information). All data were collected on an Oxford Gemini S dif-
fractometer with graphite-monochromatized MoKa radiation (l=
0.71073 Š) at 293(2) K (12, 26) and 100 K (8, 19) with oil-coated shock-
cooled crystals.[42] The structures were solved by direct methods by using
SHELXS-97[43] or SIR-92[44] and refined by full-matrix least-square proce-
dures on F2 with SHELXL-97.[45] All non-hydrogen atoms were refined
anisotropically and a riding model was employed in the refinement of the
hydrogen atom positions.
2004 (s, CO), 2060 cmꢀ1 (m, C CRu), 2116 (w, C CAu); MS (ESI-TOF)
m/z: 1944.7 [M+H]+, 749.2 [(C5H5)(dppf)Ru(CO)]+; elemental analysis
ꢁ
ꢁ
AHCTREUNG
calcd (%) for C94H77AuFeN4O3P3ReRu (1943.68): C 58.09, H 3.99, N
2.88; found: C 58.52, H 4.29, N 2.60.
CCDC-669322 (8), 669323 (12), 669324 (19), and 669325 (26) contain the
supplementary crystallographic data for this paper. These data can be ob-
tained free of charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif.
ꢁ
Preparation of [(tBu2bpy)(CO)3ReC C-bpy] (26): Complex 25 was dis-
solved in dichloromethane and left for 3 days at room temperature. The
formed precipitate was filtered off and from the filtrate pure 26 could be
isolated. Crystallization was achieved by diffusion of n-pentane into a di-
chloromethane solution containing 26. 1H NMR (250 MHz, CDCl3,
258C): d=1.46 (s, 18H; tBu), 7.19 (ddd, 3JH5’H4’ =7.6 Hz, 3JH5’H6’ =4.7 Hz,
4JH5’H3’ =1.0 Hz, 1H; H5’/bpy), 7.36 (dd, 3JH4H3 =8.2 Hz, 4JH4H6 =2.2 Hz,
1H; H4/bpy), 7.48 (dd, JH5H6 =5.8 Hz, JH5H3 =1.9 Hz, H5/tBu2bpy), 7.71
(ddd, 3JH4’H3’ =8.0 Hz, 3JH4’H5’ =7.6 Hz, 4JH4’H6’ =1.7 Hz, 1H; H4’/bpy), 8.03
(dd, 3JH3H4 =8.2 Hz, 5JH3H6 =1.0 Hz, 1H; H3/bpy), 8.10 (d, JH3H5 =1.9 Hz,
H3/tBu2bpy), 8.15 (dd, 4JH6H4 =2.2 Hz, 5JH6H3 =1.0 Hz, 1H; H6/bpy), 8.22
(ddd, 3JH3’H4’ =8.0 Hz, 4JH3’H5’ =1.0 Hz, 5JH3’H6’ =1.0 Hz, 1H; H3’/bpy), 8.58
(ddd, 3JH6’H5’ =4.7 Hz, 4JH6’H4’ =1.7 Hz, 5JH6’H3’ =1.0 Hz, 1H; H6’/bpy),
9.00 ppm (d, JH6H5 =5.8 Hz, 2H; H6/tBu2bpy); IR (NaCl): n˜ =1888, 1903,
Acknowledgement
We are grateful for generous financial support from the Deutsche For-
schungsgemeinschaft and the Fonds der Chemischen Industrie.
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2003 (s, CO), 2091cm ꢀ1 (m, C CRe).
ꢁ
5
ꢁ
Preparation
of
1-[(h2-dppf)
A
2
ꢁ
ꢁ
ReC C]-5-[PPh AuC C-bpy(Mo(CO)4)]C6H3 (28): A single portion of
27 (7 mg, 0.023 mmol) was added to a solution of 25 (45 mg, 0.023 mmol)
in a mixture of dichloromethane/THF (5:1, 10 mL). The resulting solu-
tion was stirred for 15 h at ambient temperature. Subsequently, the sol-
vent was reduced in volume to about 2 mL. On addition of diethyl ether
(10 mL), a red solid precipitated, which was washed with diethyl ether
(2”10 mL) and was then dried using an oil pump vacuum. Please note
that NMR spectroscopic investigations showed that 28 partly decom-
posed. For this reason complex 28 could not be obtained in pure form,
but could be unequivocally identified. 31P{1H} NMR (101.25 MHz,
CDCl3, 258C): d=40.8 (AuPPh2), 53.7 ppm (dppf); MS (ESI-TOF): m/z:
2152.8 [M+H]+, 749.2 [(C5H5)(dppf)Ru(CO)]+; elemental analysis calcd
N
(%) for C98H77AuFeMoN4O7P3ReRu (2151.66): C 54.71, H 3.61, N 2.60;
found: C 54.08, H 3.67, N 2.39.
5
Preparation
of
[1-{(h2-dppf)
ꢁ
(h -C5H5)RuC C}-3-{(tBu2bpy)(CO)3
ꢁ
ꢁ
ꢁ
ReC C}-5-{PPh2AuC C-bpy({[Ti](m-s,p-C CSiMe3)2}Cu)}C6H3]
A
(30): A single portion of 25 (60 mg, 0.031mmol) was added to 29 (25 mg,
0.033 mmol) dissolved in THF (25 mL). The resulting reaction solution
was stirred for 2 h at 258C, whereby the color of the solution changed
from orange to red. Subsequently, the solvent was reduced in volume
under reduced pressure and the product 30 was precipitated by addition
of n-hexane (20 mL). The precipitate was washed with n-hexane (2”
10 mL) and was then dried using an oil pump vacuum. Complex 30 could
be obtained as an orange red solid. Yield:70 mg (0.026 mmol, 85%).
1H NMR (250 MHz, CDCl3, 258C): d=ꢀ0.50 (s, 18H; SiMe3), 0.27 (brs,
18H; SiMe3), 1.41 (s, 18H; tBu), 3.93 (dpseudo-t,
JHP =1Hz, JHH =
2.4 Hz, 2H; C5H4), 4.02 (bs, 2H; C5H4), 4.20 (s, 5H; C5H5), 4.25 (bs, 2H;
C5H4), 5.00 (brs, 2H; C5H4), 6.23–6.30 (m, 8H; C5H4/CpTMS), 6.83
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+ 2H (H5/tBu2bpy)), 7.62–7.75 (m, 4H (C6H5) + 1 H (H5’/bpy)), 8.12
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4958
www.chemeurj.org
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2008, 14, 4948 – 4960

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Received: December 5, 2007
Published online: April 16, 2008
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