Heterotrimetallic and heterotetrametallic transition metal complexes

Article abstract of DOI:10.1016/j.jorganchem.2007.11.052

The synthesis of the ruthenium σ-acetylides (η⁵-C₅H₅)L₂Ru-C{triple bond, long}C-bipy (4a, L = PPh₃; 4b, L₂ = dppf; bipy = 2,2′-bipyridine-5-yl; dppf = 1,1′-bis(diphenylphosphino)ferrocene) is possible by the reaction of [(η⁵-C₅H₅)L₂RuCl] (1) with 5-ethynyl-2,2′-bipyridine (2a) in the presence of NH₄PF₆ followed by deprotonation with DBU. Heterobimetallic Fc-C{triple bond, long}C-NCN-Pt-C{triple bond, long}C-R (10a, R = bipy; 10b, R = C₅H₄N-4; Fc = (η⁵-C₅H₅)(η⁵-C₅H₄)Fe; NCN = [1,4-C₆H₂(CH₂NMe₂)₂-2,6]^-) is accessible by the metathesis of Fc-C{triple bond, long}C-NCN-PtCl (9) with lithium acetylides LiC{triple bond, long}C-R (2a, R = bipy; 2b, R = C₅H₄N-4).The complexation behavior of 4a and 4b was investigated.Treatment of these molecules with [MnBr(CO)₅] (13) and {[Ti](μ-σ,π-C{triple bond, long}CSiMe₃)₂}MX (15a, MX = Cu(N{triple bond, long}CMe)PF₆; 15b, MX = Cu(N{triple bond, long}CMe)BF₄; 16, MX = AgOClO₃; [Ti] = (η⁵-C₅H₄SiMe₃)₂Ti), respectively, gave the heteromultimetallic transition metal complexes (η⁵- C₅H₅)L₂Ru-C{triple bond, long}C-bipy[Mn(CO)₃Br] (14a: L = PPh₃; 14b: L₂ = dppf) and [(η⁵-C₅H₅)L₂Ru-C{triple bond, long}C-bipy{[Ti](μ-σ,π-C{triple bond, long}CSiMe₃)₂}M]X (17a: L = PPh₃, M = Cu, X = BF₄; 17b: L₂ = dppf, M = Cu, X = PF₆; 18a: L = PPh₃, M = Ag, X = ClO₄; 18b: L₂ = dppf, M = Ag, X = ClO₄) in which the appropriate transition metals are bridged by carbon-rich connectivities. The solid-state structures of 4b, 10b, 12 and 17b are reported. The main structural feature of 10b is the square-planar-surrounded platinum(II) ion and its linear arrangement. In complex 12 the N-atom of the pendant pyridine unit coordinates to a [mer,trans-(NN′N)RuCl₂] (NN′N = 2,6-bis-[(dimethylamino)methyl]pyridine) complex fragment, resulting in a distorted octahedral environment at the Ru(II) centre. In 4b a 1,1′-bis(diphenylphosphino)ferrocene building block is coordinated to a cyclopentadienylruthenium-σ-acetylide fragment. Heterotetrametallic 17b contains a (η⁵-C₅H₅)(dppf)Ru-C{triple bond, long}C-bipy unit, the bipyridine entity of which is chelate-bonded to [{[Ti](μ-σ,π-C{triple bond, long}CSiMe₃)₂}Cu]⁺. Within this arrangement copper(I) is tetra-coordinated and hence, possesses a pseudo-tetrahedral coordination sphere. The electrochemical behavior of 4, 10b, 12, 17 and 18 is discussed. As typical for these molecules, reversible oxidation processes are found for the iron(II) and ruthenium(II) ions. The attachment of copper(I) or silver(I) building blocks at the bipyridine moiety as given in complexes 17 and 18 complicates the oxidation of ruthenium and consequently the reduction of the group-11 metals is made more difficult, indicating an interaction over the organic bridging units. The above described complexes add to the so far only less investigated class of compounds of heteromultimetallic carbon-rich transition metal compounds.

Full text of DOI:10.1016/j.jorganchem.2007.11.052

Available online at www.sciencedirect.com
Journal of Organometallic Chemistry 693 (2008) 933–946
www.elsevier.com/locate/jorganchem
Heterotrimetallic and heterotetrametallic transition metal complexes
Rico Packheiser, Petra Ecorchard, Bernhard Walfort, Heinrich Lang *
Technische Universita¨t Chemnitz, Fakulta¨t fu¨r Naturwissenschaften, Institut fu¨r Chemie, Lehrstuhl fu¨r Anorganische Chemie,
Straße der Nationen 62, 09111 Chemnitz, Germany
Received 1 October 2007; received in revised form 22 November 2007; accepted 28 November 2007
Available online 4 December 2007
Abstract
The synthesis of the ruthenium r-acetylides (g5-C5H5)L2Ru–C„C–bipy (4a, L = PPh3; 4b, L2 = dppf; bipy = 2,20-bipyridine-5-yl;
dppf = 1,10-bis(diphenylphosphino)ferrocene) is possible by the reaction of [(g5-C5H5)L2RuCl] (1) with 5-ethynyl-2,20-bipyridine (2a)
in the presence of NH4PF6 followed by deprotonation with DBU. Heterobimetallic Fc–C„C–NCN–Pt–C„C–R (10a, R = bipy;
10b, R = C5H4N-4; Fc = (g5-C5H5)(g5-C5H4)Fe; NCN = [1,4-C6H2(CH2NMe2)2-2,6]ꢀ) is accessible by the metathesis of Fc–C„C–
NCN–PtCl (9) with lithium acetylides LiC„C–R (2a, R = bipy; 2b, R = C5H4N-4).The complexation behavior of 4a and 4b was inves-
tigated.Treatment of these molecules with [MnBr(CO)5] (13) and {[Ti](l–r,p-C„CSiMe3)2}MX (15a, MX = Cu(N„CMe)PF6; 15b,
MX = Cu(N„CMe)BF4; 16, MX = AgOClO3; [Ti] = (g5-C5H4SiMe3)2Ti), respectively, gave the heteromultimetallic transition metal
complexes (g5- C5H5)L2Ru–C„C–bipy[Mn(CO)3Br] (14a: L = PPh3; 14b: L2 = dppf) and [(g5-C5H5)L2Ru–C„C–bipy{[Ti](l–r,p-
C„CSiMe3)2}M]X (17a: L = PPh3, M = Cu, X = BF4; 17b: L2 = dppf, M = Cu, X = PF6; 18a: L = PPh3, M = Ag, X = ClO4; 18b:
L2 = dppf, M = Ag, X = ClO4) in which the appropriate transition metals are bridged by carbon-rich connectivities.
The solid-state structures of 4b, 10b, 12 and 17b are reported. The main structural feature of 10b is the square-planar-surrounded
platinum(II) ion and its linear arrangement. In complex 12 the N-atom of the pendant pyridine unit coordinates to a [mer,trans-
(NN0N)RuCl2] (NN0N = 2,6-bis-[(dimethylamino)methyl]pyridine) complex fragment, resulting in a distorted octahedral environment
at the Ru(II) centre. In 4b a 1,10-bis(diphenylphosphino)ferrocene building block is coordinated to a cyclopentadienylruthenium-r-acet-
ylide fragment. Heterotetrametallic 17b contains a (g5-C5H5)(dppf)Ru–C„C–bipy unit, the bipyridine entity of which is chelate-bonded
to [{[Ti](l–r,p-C„CSiMe3)2}Cu]+. Within this arrangement copper(I) is tetra-coordinated and hence, possesses a pseudo-tetrahedral
coordination sphere.
The electrochemical behavior of 4, 10b, 12, 17 and 18 is discussed. As typical for these molecules, reversible oxidation processes are
found for the iron(II) and ruthenium(II) ions. The attachment of copper(I) or silver(I) building blocks at the bipyridine moiety as given in
complexes 17 and 18 complicates the oxidation of ruthenium and consequently the reduction of the group-11 metals is made more dif-
ficult, indicating an interaction over the organic bridging units.
The above described complexes add to the so far only less investigated class of compounds of heteromultimetallic carbon-rich tran-
sition metal compounds.
Ó 2007 Elsevier B.V. All rights reserved.
Keywords: Ruthenium; Platinum; Copper; Silver; Acetylide; Ferrocene
1. Introduction
complexes, a hitherto scarcely explored class of com-
pounds, is an important theme within contemporary orga-
nometallic chemistry [1]. One approach to verify this
subject is given by using the concept of molecular ‘‘Tinkert-
oys”, which was independently established by Michl and
Stoddart [2,3]. Individually functionalized multitopic inor-
ganic, organic, organometallic and/or metal-organic mole-
cules can be considered as modular building blocks and can
The covalent and dative linkage of metal complex frag-
ments to generate heteromultimetallic transition metal
*
Corresponding author. Tel.: +49 371 531 21210; fax: +49 371 531
21219.
E-mail address: heinrich.lang@chemie.tu-chemnitz.de (H. Lang).
0022-328X/$ - see front matter Ó 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2007.11.052

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R. Packheiser et al. / Journal of Organometallic Chemistry 693 (2008) 933–946
successfully be assembled to a specific building design to
give complexes of higher nuclearity with novel structures.
Such molecules may show unique and often unusual
properties.
In context with this background, we focus here on the
use of alkynyl-functionalized ferrocenes, bis(alkynyl)
titanocenes, NCN pincer molecules (NCN = [4-X–
C6H2(CH2NMe2)2-2,6]ꢀ; X = C„C, . . .), and alkynyl-
substituted pyridine ligands as building blocks in the
synthesis of heterotri- and heterotetrametallic systems in
which the appropriate transition metals are connected by
carbon-rich bridging units.
appearance of two 31P{1H} NMR resonance signals as well
as a mC„C and mC@C vibration in the IR spectra. It is most
likely that a vinylidene complex is formed as the primary
product, which is then converted to a pyridinium system
[5]. Removal of the vinylidene b-hydrogen atom or the
bipyridine-bonded proton by methoxide or DBU
(DBU = 1,8-diazabicyclo[5.4.0]undec-7-ene) caused the
formation of the ruthenium r-acetylides 4a and 4b contain-
ing a pendant 2,20-bipyridine-5-yl entity, which is capable
of coordinating to different transition metal fragments
and consequently is suitable for the construction of transi-
tion metal complexes of higher nuclearity.
Another molecule with a multitopic ligand allowing to
introduce further metal-containing building blocks is Fc–
C„C–NCN–Pt–C„C–R (10a, R = bipy; 10b, R =
C5H4N-4; Fc = (g5-C5H5)(g5-C5H4)Fe; NCN = [C6H2
(CH2NMe2)2-2,6]ꢀ). The preparation of this molecule is
shown in Scheme 2 and includes several consecutive steps.
Heterobimetallic Fc–C„C–NCN–Pt–C„C–R (10a,
R = bipy; 10b, R = C5H4N-4) is accessible by a consecutive
synthesis methodology including carbon–carbon cross-cou-
pling, lithiation, trans-metallation, and metathesis reac-
tions. Following the Sonogashira cross-coupling protocol
[6], Fc–C„C–NCNH (7) (NCNH = 1-C6H3(CH2NMe2)2-
3,5) was prepared by reacting ethynylferrocene (5) with
I-1-C6H3(CH2NMe2)2-3,5 (6) in the presence of
[(Ph3P)2PdCl2/CuI] and diisopropylamine as solvent [7].
A possibility to introduce a platinum chloride entity into
NCN pincer molecules is given by a lithiation–trans-metal-
lation procedure: lithiation of 7 with nBuLi and subsequent
treatment of the respective lithium salt with [(Et2S)2PtCl2]
(8) produced heterobimetallic Fc–C„C–NCN–PtCl (9)
[7], which further reacted with in-situ lithiated HC„C–R
(2a, R = bipy; 2b, R = C5H4N-4) to give the title com-
plexes 10a and 10b, respectively (Scheme 2). However,
compound 10a was always obtained together with small
amounts of unreacted 9, even when Li–2a was used in a
2. Results and discussion
2.1. Synthesis and characterization
The synthesis of two new mono- and heterobimetallic
rutheniumacetylide complexes with a pendant 2,20-bipyri-
dine-5-yl unit (=bipy) can be realized as shown in Scheme
1. Addition of 5-ethynyl-2,20-bipyridine (2a) to the ruthe-
nium(II) complex [(g5-C5H5)L2RuCl] (1a, L = PPh3; 1b,
L2 = dppf (dppf = 1,10-bis(diphenylphosphino)ferrocene))
in the presence of NH4PF6 in a 1:1 mixture of dichloro-
methane and methanol resulted in the formation of yellow
(g5-C5H5)L2Ru–C„C–bipy (4a, L = PPh3; 1b, L2 = dppf).
Within the reaction of terminal alkynes with coordinatively
unsaturated metal complexes, metal vinylidene transition
metal species (3a, 3b, Scheme 1) are ubiquitous formed as
intermediates [4]. When 1 is treated with the terminal
alkyne 2a, due to the intrinsic basicity of the bipyridine
moiety, a somewhat different behavior is observed as com-
pared with those of regular terminal alkynes. Next to the
expected
ruthenium
vinylidene
[(g5-C5H5)L2Ru
@C@C(H)(bipy)]+ (3a) also the r-acetylide complex [(g5-
C5H5)L2Ru–C„C–bipyH]+ (3b) with a pendant pyridini-
um unit was produced (Scheme 1), as evidenced by the
Ru Cl
HC C
Ru C C
+
L
L
N
N
N
N
L
L
2a
1a, 1b
4a, 4b
DBU
CH2Cl2,
MeOH
NH4PF6
4a: L = PPh3
4b: L2 =
Thf
PPh2
PPh2
H
C
Fe
PF6
Ru
C
L
Ru C C
L
L
N
N
L
N
H
N
3a, 3b
Scheme 1. Synthesis of 4a and 4b from 1a, 1b and 2a by the intermediate formation of 3a and 3b, respectively.

R. Packheiser et al. / Journal of Organometallic Chemistry 693 (2008) 933–946
935
NMe2
NMe2
I
(6)
C C
C CH
NMe2
Fe
Fe
[(Ph3P)2PdCl2]/[CuI]
NMe2
7
5
NMe2
Pt Cl
NMe2
NMe2
1. nBuLi
2. (Et2S)2PtCl2 (8)
C C
C C
Pt C C
NMe2
R
LiC CR
Fe
Fe
9
10a: R =
10b: R =
N
N
N
Scheme 2. Preparation of the heterobimetallic Fe–Pt complexes 10a and 10b.
twofold excess. Because a separation of 10a from 9 was not
possible, no further reactions were carried out with this
compound.
When 10b was reacted with the dinitrogen-bridged di-
ruthenium complex [Ru]N„N[Ru] (11) ([Ru] = [g3-mer-
{2,6-(Me2NCH2)2C5H3N}RuCl2]) [8], the formation of
neutral heterotrimetallic 12 occured by the liberation of
N2 (Eq. (1)). The reaction could be followed visually by
the change of the color of the reaction solution from yellow
to intense red.
containing these molecules are somewhat sensitive to oxy-
gen and moisture, especially those containing the mono-
dentate triphenylphosphine ligands at ruthenium.
In the newly synthesized complexes 10, 12, 14, 17 and 18
different transition metal atoms such as titanium, manga-
nese, ruthenium, iron, platinum and copper are brought
in close proximity to each other by carbon-rich bridging
units.
Complexes 4, 10, 12, 14, 17 and 18 were fully character-
ized by elemental analysis, IR- and NMR spectroscopy
Me2N
Cl
NMe2
[Ru]N N[Ru] (11)
Ru
N
C C
Pt C C
NMe2
12
N
10b
ð1Þ
Fe
Cl
Me2N
- N2
Complexes 4a and 4b possess with their terminal bipyridine
unit a further N-ligating site which should allow to success-
fully introduce further transition metal entities.
(1H, 13C{1H}, 31P{1H}), while 10a, 10b and 12 were further
characterized by mass spectrometry. Complexes 4b, 10b
and 17b were additionally subjected to single crystal
X-ray structure determination.
Thus, these compounds were reacted with [MnBr(CO)5]
(13) and the heterobimetallic organometallic p-tweezer
{[Ti](l–r,p-C„CSiMe3)2}MX (15a, MX = Cu(N„C-
Me)PF6; 15b, MX = Cu(N„CMe)BF4; 16, MX = AgO-
ClO3; [Ti] = (g5-C5H4SiMe3)2Ti) in ethanol (synthesis of
14a, 14b) or tetrahydrofuran (synthesis of 17 and 18),
whereby the CO and acetonitrile ligands in 13 and 15 were
replaced by the bidenate donor 2,20-bipyridine (Scheme 3).
The appropriate reactions resulted in a color change from
yellow to red. After appropriate work-up, complexes 14,
17 and 18 could be isolated in good yield as orange-red sol-
ids (Section 4). They are soluble in, for example, dichloro-
methane, chloroform and tetrahydrofuran. Solutions
Most characteristic in the IR spectra of 4, 14, 17 and 18 is
the appearance of a sharp absorption band which can be
assigned to the ruthenium-bonded acetylide unit. For 4a
and 4b this mC„C vibration is found at ca. 2070 cmꢀ1, while
in complexes 14, 17 and 18 in which the bipyridine unit
coordinates to MnBr(CO)3 and [{[Ti](l–r,p-C„CSi-
Me3)2}M]+, respectively, this band is shifted by 30 cmꢀ1
to lower wavenumbers. This points to a weaker carbon–
carbon triple bond and is typical for similar compounds
in which nitrogen-containing ligands are coordinated to a
MLn transition metal fragment or are protonated, i.e.
(g5-C5H5)(PPh3)2Ru–C„C–C5H4N-[W(CO)5] [5]. Further

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R. Packheiser et al. / Journal of Organometallic Chemistry 693 (2008) 933–946
Ru C C
L
N
N
L
13
OC Mn Br
OC
CO
14a, 14b
Ru C C
L
N
N
L
4a, 4b
15, 16
Ru
C
C
X
a: L = PPh3
b: L2 =
L
N
N
L
Me3Si
SiMe3
M
Ti
PPh2
PPh2
C
C
Fe
C
C
Me3Si
SiMe3
17a: L = PPh3, M = Cu, X = BF4
17b: L2 = dppf, M = Cu, X = PF6
18a: L = PPh3, M = Ag, X = ClO4
18b: L2 = dppf, M = Ag, X = ClO4
Scheme 3. Synthesis of heterotri- and heterotetrametallic 14, 17 and 18.
representative bands which can be observed are the
carbonyl vibrations in 14 and the mC„C band for the
Ti–C„C unit in 17 and 18 (Section 4). The three strong car-
bonyl stretching absorptions in 14a and 14b are characteris-
tic for this type of metal carbonyl building block [9]. For the
iron–platinum molecules 10a, 10b and 12 two stretching fre-
quencies at ca. 2210 (mC„CFc) and 2078 cmꢀ1 (mC„CPt) are
found, which is consistent with the two different alkynyl
carbon–carbon triple bonds present (Section 4) [7,10].
The NMR spectroscopic properties of 4, 14, 17 and 18
are consistent with their formulations as heterometallic
NMR spectra of these compounds show resonance signals
in the aromatic region typical for pyridine, bipyridine, and
phenyl groups. Due to the different chemical environment,
the dppf cyclopentadienyl protons appear as four separated
signals, whereby three of them are found between 4.0 and
4.4 ppm and the other is located at ca. 5.1 ppm. The coor-
dination of the bipyridine ligand to the respective metal
atoms can be verified by the shift of the resonance signals
of the bipyridine protons, i.e., due to the coordination of
the bipyridine moiety to manganese the protons H6 and
H60, which are located next to the nitrogen atoms, are
shifted from 8.42 (H6) and 8.64 ppm (H60) in 4a to 8.86
1
ruthenium acetylide-based complexes (Section 4). The H
Fig. 1. ORTEP drawing of 10b. Thermal ellipsoids are shown at 50% probability level. The hydrogen atoms are omitted for clarity. Selected bond lengths
˚
(A) and angles (°): C1–C11, 1.445(6); C11–C12, 1.187(7); C12–C13, 1.448(6); C16–Pt1, 1.949(4); Pt1–N1, 2.091(3); Pt1–N2, 2.093(3); Pt1–C25, 2.062(4);
C25–C26, 1.202(7); C26–C29, 1.433(7); Fe1–D1, 1.6433(2); Fe1–D2, 1.6533(2); C1–C11–C12, 178.1(5); C11–C12–C13, 177.1(5); C16–Pt1–C25, 177.84(17);
Pt1–C25–C26, 178.9(4); C25–C26–C29, 176.4(5); N1–Pt1–N2, 163.06(14); C16–Pt1–N1, 81.35(16); C16–Pt1–N2, 81.71(16); N1–Pt1–C25, 98.74(15); N2–
Pt1–C25, 98.19(15); (D1 = centroid of C5H4; D2 = centroid of C5H5).

R. Packheiser et al. / Journal of Organometallic Chemistry 693 (2008) 933–946
937
1
(H6) and 9.16 ppm (H60) in 14a [9,11]. Notable in the H
NMR spectra of 17 and 18, when compared with 15 and
16, is the highfield shift of the Me3SiC„C protons from
ca. 0.25 ppm (15) to ꢀ0.45 (17) and ꢀ0.28 ppm (18),
respectively, which can be explained by the ring current
of the bipyridine ligand [11]. Furthermore, 17a and 17b
show two separated resonance signals for the Me3Si pro-
tons of the titanium-bonded cyclopentadienyl ligands
which is attributed to their unsymmetrical chemical envi-
ronment (Section 4) [11]. The protons of the Me2NCH2
pincer arms in 10 are observed at ca. 3.20 (NMe2) and
4.12 ppm (CH2) showing typical 195Pt satellites with cou-
3
pling constants of ca. 40 Hz (3JPtH(Me) and JPtH(CH2)
)
[7,10]. The successful formation of 12 is evidenced by a
Fig. 2. ORTEP drawing of one of the two crystallographically independent molecules of 12. Thermal ellipsoids are shown at 30% probability level. The
˚
hydrogen atoms and the three dichloromethane solvent molecules are omitted for clarity. Selected bond lengths (A) and angles (°): C1–C11, 1.420(19);
C11–C12, 1.189(19); C12–C13, 1.463(19); C16–Pt1, 1.949(13); Pt1–N1, 2.077(10); Pt1–N2, 2.065(10); Pt1–C25, 2.026(13); C25–C26, 1.238(18); C26–C27,
1.431(17); Fe1–D1, 1.652(6); Fe1–D2, 1.642(6); Ru1–N3, 2.112(10); Ru1–N4, 1.981(11); Ru1–N5, 2.212(11); Ru1–N6, 2.187(12); Ru1–Cl1, 2.413(4); Ru1–
Cl2, 2.421(3); C1–C11–C12, 174.5(15); C11–C12–C13, 178.1(15); C16–Pt1–C25, 173.6(5); Pt1–C25–C26, 171.7(11); C25–C26–C27, 174.8(14); N1–Pt1–N2,
162.3(4); C16–Pt1–N1, 81.4(5); C16–Pt1–N2, 81.0(5); N1–Pt1–C25, 98.6(4); N2–Pt1–C25, 99.1(5); N3–Ru1–N4, 178.4(5); N5–Ru1–N6, 158.6(4); Cl1–
Ru1–Cl2, 177.81(12); N3–Ru1–N5, 99.4(4); N3–Ru1–N6, 102.0(4); N4–Ru1–N5, 79.1(5); N4–Ru1–N6, 79.5(5); (D1 = centroid of C5H4; D2 = centroid of
C5H5).
Fig. 3. ORTEP drawing of 4b. Thermal ellipsoids are shown at 50% probability level. The hydrogen atoms and the non-coordinated dichloromethane
˚
solvent molecule are omitted for clarity. Selected bond lengths (A) and angles (°): Ru1–P1, 2.2677(5); Ru1–P2, 2.2774(5); Ru1–C40, 2.0029(18); C40–C41,
1.208(3); C41–C43, 1.429(2); Ru1–D1, 1.8888(8); Fe1–D2, 1.6413(8); Fe1–D3, 1.6391(8); P1–Ru1–P2, 97.061(17); Ru1–C40–C41, 173.04(15); C40–C41–
C43, 176.7(2) (D1 = centroid of C5H5; D2 = centroid of C1–C5; D3 = centroid of C6–C10).

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R. Packheiser et al. / Journal of Organometallic Chemistry 693 (2008) 933–946
downfield shift of the pyridine protons adjacent to nitrogen
by 1.0 ppm. The pincer ligand at ruthenium additionally
shows the expected resonance signals [12].
the legends of Figs. 1–4, while the crystal and structure
refinement data are summarized in Table 1 (Section 4).
Single crystals of 10b for X-ray structure analysis were
obtained by layering a dichloromethane/acetonitrile solu-
tion containing 10b with n-pentane. Complex 10b crystal-
lizes in the monoclinic space group P21/n. The main
structural features resemble the structural data characteris-
tic for ferrocene and NCN pincer complexes [7,15,16]. Con-
sistent with other ferrocene complexes the Fe1–D1 and
Fe1–D2 separations are found with 1.6433(2) and
The 31P{1H} NMR spectra of all ruthenium–acetylide
complexes display one resonance signal at ca. 49 or
54 ppm, due to the presence of the PPh3 or dppf units
[4,5,13]. Coordination of the bipyridine ligand to the
respective transition metal fragments in 14, 17 and 18 does
not significantly influence the position of these signals (Sec-
tion 4).
˚
The identity of heterobimetallic 10a and 10b and hetero-
trimetallic 12 was additionally evidenced from the mass
spectrometric investigations. The electrospray ionization
mass spectra (ESI MS) show the molecular ion peaks at
1.6533(2) A [15]. The two cyclopentadienyl ligands are
rotated by 2.35(9)° to each other, which verifies an almost
eclipsed conformation.
The Pt1 atom adopts a distorted square-planar geome-
try set-up by C16, N1, N2 and C25 (r.m.s. deviation
a
mass-to-charge ratio of 774.4 [10a+H]+, 697.3
[10b+H]+ and 1062.4 [12+H]+. The mass and isotope dis-
0.0168 A). The C16–Pt1–C25 bond angle is with
˚
tribution patterns comply to the formulated structures.
177.84(17)° almost linear, while the N1–Pt1–N2 angle with
163.06(14)° deviates from linearity. The C„C functional-
ities are as expected linear (C1–C11–C12, 178.1(5)°; C11–
C12–C13, 177.1(5)°; Pt1–C25–C26, 178.9(4)°; C25–C26–
C29, 176.4(5)°). Notable is the angle between the planes
of the C6H2 unit, the pyridine entity and the g5-coordi-
nated C5H4 ring. For the C6H2 and the cyclopentadienyl
ring a tilting angle of 61.70(1)° is found, while between
2.2. Structural characterization
Complexes 4b, 10b, 12 and 17b were further character-
ized by single crystal X-ray diffraction studies. The molec-
ular structures of these molecules are shown in Figs. 1–4.
˚
Selected bond distances (A) and angles (°) are given in
Fig. 4. The molecular structure (ORTEP 30% probability level) of heterotetrametallic 17b with the atomic numbering scheme. Hydrogen atoms, the
ꢀ
˚
solvent molecule tetrahydrofuran and the PF6 counter ion are omitted for clarity. Selected bond distances (A) and angles (°): Ru1–P1, 2.2985(13); Ru1–
P2, 2.2758(13); Ru1–C40, 2.004(5); C40–C41, 1.200(6); C41–C43, 1.440(7); Ru1–D1, 1.9006(2); Fe1–D2, 1.6392(2); Fe1–D3, 1.6312(2); Ti1–D4, 2.0570(2);
Ti1–D5, 2.0476(2); Ti1–C52, 2.101(5); Ti1–C57, 2.091(5); C52–C53, 1.227(6); C57–C58, 1.237(6); Cu1–N1, 2.115(4); Cu1–N2, 2.123(4); P1–Ru1–P2,
98.46(5); Ru1–C40–C41, 175.9(4); C40–C41–C43, 178.4(5); C52–Ti1–C57, 89.10(18); Ti1–C52–C53, 168.2(4); Ti1–C57–C58, 168.2(4); C52–C53–Si1,
162.6(4); C57–C58–Si2, 160.1(5); N1–Cu1–N2, 77.92(15) (D1 = centroid of C5H5; D2 = centroid of C1–C5; D3 = centroid of C6–C10; D4 = centroid of
C62–C66; D5 = centroid of C70–C74).

R. Packheiser et al. / Journal of Organometallic Chemistry 693 (2008) 933–946
939
Table 1
Crystal and intensity collection data for 4b, 10b, 12 and 17b
4b
10b
12
17b
Empirical formula
Formula weight
Crystal system
Space group
C52H42Cl2FeN2P2Ru
984.64
Monoclinic
P21/c
11.2769(5)
28.6778(13)
14.2622(7)
90
107.1530(10)
90
C31H31FeN3Pt
696.53
Monoclinic
P21/n
5.80820(10)
11.89020(10)
37.6944(3)
90
93.0220(10)
90
C88H108Cl12Fe2N12Pt2Ru2
2463.28
Triclinic
C81H92CuF6FeN2OP3RuSi4Ti
1697.20
Monoclinic
P21
16.5178(14)
14.4734(12)
17.4078(15)
90
93.195(2)
90
4155.2(6)
1.357
ꢀ
P1
˚
a (A)
12.681(2)
12.7005(13)
30.778(6)
96.359(12)
91.404(15)
92.345(11)
4920.4(14)
1.663
˚
b (A)
˚
c (A)
a (°)
b (°)
c (°)
3
˚
V (A )
4407.2(4)
1.484
2599.58(5)
1.780
qcalc (g cmꢀ3
)
F(000)
2008
1368
2440
1752
Crystal dimensions (mm3)
0.5 ꢁ 0.3 ꢁ 0.1
0.5 ꢁ 0.2 ꢁ 0.2
0.5 ꢁ 0.2 ꢁ 0.1
0.3 ꢁ 0.2 ꢁ 0.03
Z
4
4
2
2
Maximum, minimum transmission
0.99999, 0.847974
0.905
1.42–27.10
ꢀ14 6 h 6 13,
0 6 k 6 36, 0 6 l 6 18
1.00000, 0.25740
14.576
1.00000, 0.18909
13.281
0.99999, 0.781845
0.867
1.65–26.38
ꢀ20 6 h 6 20, ꢀ18 6 k 6 18,
Absorption coefficient (l, mmꢀ1
Scan range (°)
)
3.90–60.51
ꢀ6 6 h 6 6,
ꢀ13 6 k 6 13,
ꢀ42 6 l 6 42
18,805
3.49–60.25
ꢀ14 6 h 6 13,
Index ranges
ꢀ14 6 k 6 14, ꢀ34 6 l 6 34 0 6 l 6 21
Total reflections
53,441
33,523
47,881
Unique reflections
Rint
9946
0.0260
3918
0.0291
14,248
0.0477
17,026
0.0616
Data/restraints/parameters
Goodness-of-fit on F2
R1,a wRa2 [I P 32r(I)]
R1,a wRa2 (all data)
9725/0/541
1.039
0.0263, 0.0635
0.0311, 0.0662
0.832, ꢀ0.922
3918/24/325
1.203
0.0278, 0.0694
0.0284, 0.0697
1.015, ꢀ0.991
14248/96/1119
1.079
0.0708, 0.1744
0.0842, 0.1813
3.900, ꢀ1.596
17005/46/922
1.014
0.0436, 0.0851
0.0810, 0.0995
0.387, ꢀ0.402
Maximum, minimum peak in final
ꢀ3
˚
Fourier map (e A
)
n, the number of reflections; p, the parameters used.
P
P
P
P
P
2
2
aR1 ¼ ½ ðkF oj ꢀ jF cjÞ= ðjF ojÞ; wR2 ¼ ½ ðwðF o2 ꢀ F c2Þ Þ= ðwF 4oÞꢂ1=2. S ¼ ½ wðF o2 ꢀ F 2c Þ ꢂ=ðn ꢀ pÞ1=2.
a
˚
the C6H2 moiety and the pyridine unit an angle of 83.34(1)°
pared to that of Ru1–N4 (1.981(11) A), but both lie in
the range of distances reported for other ruthenium(II)–
pyridine complexes [17,18]. The angle N3–Ru1–N4
is typical. These orientations avert an optimal overlap
between the p-orbitals, but primarily seem to depend on
crystal packing effects.
˚
(178.4(5) A) illustrates the linearity of this array. The
Complex 12 crystallized by the diffusion of n-pentane
into a dichloromethane solution containing 12 at ꢀ30 °C
as deep red needles. Compound 12 crystallizes in the tri-
planes of the two pyridine rings form a tilting angle of
64.72(0.49)° with respect to each other. The calculated
˚
overall length of molecule 12 amounts to ca. 25.88 A
ꢀ
clinic space group P1 with two crystallographically inde-
(C9–C34).
pendent molecules in the asymmetric unit. The result of
Molecule 4b crystallizes in the monoclinic space group
P21/c. The overall structural features of 4b are similar to
those of the related structurally characterized diphenyl-
phosphino ferrocene, cyclopentadienyl ruthenium r-acety-
lides and bipyridine-containing compounds with
the X-ray diffraction study confirms the general structure
1
of 12, suggested on the basis of the IR and H NMR data.
With minor deviations the structural properties of the Fc–
C„C–NCN–Pt–C„C–C5H4N unit are comparable to that
found for 10b.
ruthenium in
a
pseudo-tetrahedral arrangement
The ruthenium(II) centre occupies a distorted octahe-
dral surrounding, with the three N-donor atoms of the
NN0N ligand in a meridional position. The introduced pyr-
idine ligand is r-coordinated via the nitrogen atom and
positioned trans to the pyridine nitrogen atom of the NN0N
ligand, a situation which forces the two chloride ligands
trans to each other in the apical positions. The Ru–Npy,
Ru–NNMe and Ru–Cl distances as well as the angles
around the Ru(II) ion (Fig. 2) are consistent with those val-
ues reported for this type of building block [17]. The Ru1–
[4,5,11,13,14]. The cyclopentadienyl rings of the dppf entity
are rotated by 2.13(4)° to each other which verifies an
almost eclipsed conformation. The ruthenium acetylide
unit Ru1–C40–C41–C43 is with 173.04(15)° (Ru1–C40–
C41) and 176.7(2)° (C40–C41–C43) almost linear. Notable
is the dppf bite angle P1–Ru1–P2 which is with 97.061(17)°
smaller than those ones found in (g5-C5H5)(Ph3P)2Ru r-
acetylides (99.01(6)–101.17(7)°), but similar to the related
(dppf)(g5-C5H5)Ru–acetylide systems [5,13]. The ruthe-
nium–phosphorus distances are with 2.2677(5) (Ru1–P1)
˚
˚
N3 bond distance (2.112(10) A) is elongated when com-
and 2.2774(5) A (Ru1–P2) characteristic of this type of

940
R. Packheiser et al. / Journal of Organometallic Chemistry 693 (2008) 933–946
˚
molecules [5,13]. The same is true for the Ru1–C40, C40–
C41 and C41–C43 separations (Fig. 3).
(N1, N2, C45–C48, Cu1; r.m.s. deviation 0.0919 A)
(Fig. 4). All other bond lengths and angles require no fur-
ther discussion, because they agree well with those param-
eters described for related transition metal complexes
[4,5,11,13,19].
Single crystals of 17b suitable for X-ray diffraction stud-
ies could be grown by the slow vapour diffusion of n-pen-
tane into a tetrahydrofuran solution containing 17b at
ꢀ30 °C. Fig. 4 shows the perspective drawing of 17b
together with the atomic numbering scheme. Heterotetra-
metallic 17b crystallizes in the monoclinic space group
P21. The molecular structure of 17b consists of a
(dppf)(g5-C5H5)Ru–C„C–bipy building block, the 1,10-
bis(diphenylphosphino)ferrocene unit of which is in a
eclipsed geometry (5.93(2)°), and the cyclopentadienyl
rings are inclined at an angle of 4.63(0.21)°. The bipyridine
moiety in 17b is chelate-bonded to the organometallic Ti–
Cu tweezer fragment [{[Ti](l–r,p-C„CSiMe3)2}Cu]+
(Fig. 4).
2.3. Cyclic voltammetry
Complexes 4, 10b, 12, 17 and 18 were investigated by
cyclic voltammetry to fathom the interaction of the metal
centers concerning their particular redox behavior. The
cyclic voltammograms of 10b and 12 (Fig. 5) show next
to the reversible redox process for iron(II) (10b:
E0 = 0.05 V, DEp = 0.11 V; 12: E0 = 0.06 V, DEp = 0.12 V)
a weak irreversible oxidation at ca. 0.65 V the origin of
which most likely arises from the oxidation of the NCN
pincer unit since this behavior has also been reported for
6 and the parent compound 9 [7,10a,20]. For heterotrime-
tallic 12 a further reversible oxidation wave is found at
E0 = ꢀ0.42 V (DEp = 0.12 V) which can be assigned to
the Ru(II)/Ru(III) oxidation. This potential is similar to
that found in {Ti}(C„C–C5H4N–[Ru]) ({Ti} = (g5-
C5H5)2Ti(CH2SiMe3)). In comparison with [Ru]–NC5H5,
the ruthenium oxidation potential of 12 is shifted to a more
negative value indicating that the oxidation is facilitated by
the presence of a platinum building block in para-position
[21]. Measuring the cyclic voltammograms upto 1.6 V
results in the appearance of an additional irreversible oxi-
dation wave at Ep,ox = 1.27 V (Fig. 5, bottom) which most
probably can be assigned to an oxidation of the 2,6-
bis[(dimethylamino)methyl]pyridine ligand at ruthenium.
The copper(I) ion possesses, as typical for this type of
compounds, a pseudo-tetrahedral arrangement [11,19].
The carbon–carbon distances of the ruthenium and tita-
nium acetylide moieties are 1.200(6) (C40–C41), 1.227(6)
˚
(C52–C53), and 1.237(6) A (C57–C58), which are compara-
ble to those of other ruthenium(II) and titanium(IV) alky-
nyls [4,5,13,19]. The respective Ru–C„C unit is essentially
linear, while the Ti–C„C–Si moieties are trans-bent as
expected for heterobimetallic [{[Ti](l–r,p-C„CSi-
Me3)2}Cu]+ organometallic p-tweezer fragments in which
a copper(I) ion is g2-coordinated by the chelating ligand
[Ti](C„CSiMe3)2 (Fig. 4) [11,19]. The {[Ti](l–r,p-
C„CSiMe3)2}Cu]+ unit (Ti1, C52, C53, C57, C58, Cu1;
˚
r.m.s. deviation 0.0371 A) is with 78.78(9)° almost perpen-
dicular oriented to the plane spanned by the bipy entity
Fig. 5. Representation of the cyclic voltammograms of 10b (top) and 12 (bottom) in three different potential ranges (10ꢀ3 M solutions in dichloromethane
at 25 °C, [n-Bu4N]PF6 supporting electrolyte (0.1 M), scan rate = 0.1 V sꢀ1; all potentials are referenced to the FcH/FcH+ redox couple with E0 = 0.00 V
[23,24]).

R. Packheiser et al. / Journal of Organometallic Chemistry 693 (2008) 933–946
941
Table 2
Electrochemical data for 1b, 4a, 4b, 17a, 17b, 18a and 18ba
Compound
Reduction
Oxidation
E0 (DEp) M(I)/M(0)
Ep,red M(I)/M(0)
E0 (DEp) Ru(II)/Ru(III)
E0 (DEp) Fe(II)/Fe(III)
Edp,ox
Edp,ox
1b
4a
0.09 (0.13)
0.07 (0.10)
0.04 (0.10)
0.215 (0.10)
0.20 (0.115)
0.205 (0.10)
0.205 (0.12)
0.42 (0.14)
0.855
0.805
4b
0.51 (0.12)
0.545 (0.165)
0.56 (0.16)
0.45
17a
17b
18a
18b
a
ꢀ1.50 (0.11)b
ꢀ1.52 (0.095)b
ꢀ1.41c
ꢀ1.41c
0.91
0.86
0.48
All potentials are given in V vs. FcH/FcH+ [23,24] from single scan cyclic voltammograms (10ꢀ3 M solutions in dichloromethane at 25 °C, [n-
Bu4N]PF6 supporting electrolyte (0.1 M), scan rate = 0.1 V sꢀ1). Detailed experimental conditions are listed in Section 4.
b
M = Cu.
M = Ag.
c
d
Irreversible or quasi-reversible redox processes that may result from the oxidation of ruthenium [13a,22].
For both complexes these measurements apparently cause
a decomposition of the molecules because no subsequent
reduction waves for iron(III) and ruthenium(III) could be
observed (Fig. 5).
The electrochemical data for 4, 17 and 18 are presented
in Table 2. The Ru(II)/Ru(III) oxidation in the ruthenium
r-acetylides 4a and 4b is found at E0 = 0.07 V (4a) and
E0 = 0.04 V (4b) with DEp = 0.10 V. While free dppf
reveals a reversible oxidation wave at E0 = 0.190 V [5], its
Fe(II)/Fe(III) oxidation is positive shifted to 0.42 V in
[(g5-C5H5)(dppf)RuCl] (1b) in which the oxidation of
Ru(II) to Ru(III) takes place at 0.09 V. Compared to that
the redox potentials of the Ru(II) and Fe(II) ions in 4b
Fig. 6. Comparison of the Ru(II)/Ru(III) redox couples of 4a (–) and 18a
show small negative and positive shifts, respectively.
Although the additionally observed oxidation processes
(---), respectively, in the oxidative region of the cyclic voltammogram
(10ꢀ3 M solutions in dichloromethane at 25 °C, [n-Bu4N]PF6 supporting
in complexes 4a and 4b are not reversible, they may origi-
nate from the oxidation of the ruthenium center, which can
be verified by a comparison to other complexes containing
(g5-C5H5)(PPh3)2Ru or (g5-C5H5)(dppf)Ru termini
[13a,22]. The Fe(II)/Fe(III) redox process in 4b could be
assigned since its potential is close to that of the iron(II)
ion in [(g5-C5H5)(dppf)RuCl] (1b) [5,13a].
electrolyte (0.1 M), scan rate = 0.1 V sꢀ1; all potentials are referenced to
the FcH/FcH+ redox couple with E0 = 0.00 V [23,24]).
is thereby only slightly affected by copper(I) or silver(I)
(Table 2). The additionally observed oxidation processes
for complexes 18a and 18b are comparable to those found
in 4a and 4b and consequently can be referred to oxidations
at the ruthenium center [13a,22]. Due to the electrochemi-
cal window of dichloromethane the expected reduction of
the pendant bipyridine unit could not be observed.
The coordination of the bipyridine ligand to a bis(alky-
nyl)titanocene–copper(I) or -silver(I) fragment as given in
complexes 17 and 18 causes a positive shift for the
Ru(II)/Ru(III) redox couple of about 0.15 V (Fig. 6).
Along with the above mentioned more difficult oxida-
tion of ruthenium in 17 and 18 as a result of the introduc-
tion of the p-tweezer building block, consequently the
reduction of the Cu(I) and Ag(I) centers is somewhat differ-
ent and hence, more complicated. This is illustrated by a
shift of the reduction current peak to a more negative value
(Table 2), when compared with, for example, [FcC„C–
bipy{[Ti](l–r,p-C„CSiMe3)2}M]X (M = Cu, X = PF6:
E0 = ꢀ1.39 V (DEp = 0.12 mV); M = Ag, X = ClO4:
Ep,red = ꢀ1.26 V) [11].
3. Conclusions
A series of heterometallic complexes with two, three,
and four different transition metal atoms, such as titanium,
manganese, iron, ruthenium, platinum, and copper is
described. Following organometallic species (g5-C5H5)
L2Ru–C„C–bipy (L = PPh3, L2 = dppf; bipy = 2,20-
bipyridine-5-yl; dppf = 1,10-bis(diphenylphosphino)ferro-
cene), Fc–C„C–NCN–Pt–C„C–R (R = bipy, C5H4N-4;
Fc = (g5-C5H5)(g5-C5H4)Fe; NCN = [C6H2(CH2NMe2)2-
2,6]ꢀ), Fc–C„C–NCN–Pt–C„C–C5H4N–[Ru] ([Ru] =
[g3-mer-{2,6-(Me2NCH2)2C5H3N}RuCl2]), (g5-C5H5)L2
Ru–C„C–bipy[Mn(CO)3Br] and (g5-C5H5)L2Ru–C„C–
bipy[{[Ti](l–r,p-C„CSiMe3)2}M]X (M = Cu, Ag; X =
This observation also corresponds to the IR data of
these systems, where, compared to 4, a decreased electron
density at the RuC„C moiety is present in 17 and 18,
which is evidenced by a shift of the mC„C vibration to lower
wavenumbers. The Fe(II)/Fe(III) oxidation in 17b and 18b

942
R. Packheiser et al. / Journal of Organometallic Chemistry 693 (2008) 933–946
PF6, BF4, ClO4) were prepared by combining different
organic and organometallic building blocks of lower nucle-
arity from a ligand and coordination complex library par-
ticularly designed and built up for this purpose. In these
species the appropriate transition metals are connected by
carbon-rich bridging units based on alkynyls, cyclopenta-
dienyl and bipyridine moieties. These complexes add to
the so far only less investigated family of heteromultimetal-
lic transition metal complexes.
FLASHEA 1112 Series (Thermo) by the Department of
Inorganic Chemistry at Chemnitz, Technical University.
4.2. General remarks
(g5-C5H5)(PPh3)2RuCl [26], (g5-C5H5)(dppf)RuCl [27],
5-ethynyl-2,20-bipyridine [28], 4-ethynylpyridine [29], [Ru]
N„N[Ru] [8], Mn(CO)5Br [30], [{[Ti](l–r,p-C„CSi-
Me3)2}Cu(N„CMe)]PF6 [31], [{[Ti](l–r,p-C„CSiMe3)2}-
Investigation of the redox chemistry of the selected com-
plexes revealed an electronic influence of the appropriate
metal building blocks on each other, which could be dem-
onstrated by cyclic voltammetry.
Cu(N„CMe)]BF4
[31],
{[Ti](l–r,p-C„CSiMe3)2}
AgOClO3 [32], Fc–C„C–NCNH [7] and Fc–C
„C–NCNPtCl [7] were prepared following published pro-
cedures. All other chemicals were purchased from commer-
cial suppliers and were used as received.
4. Experimental
4.3. Synthesis of (g5-C5H5)(PPh3)2Ru–C„C–bipy (4a)
4.1. General methods
About 160 mg (0.89 mmol) of 5-ethynyl-2,20-bipyridine
(2) dissolved in MeOH (20 mL) was added to 600 mg
(0.83 mmol) of (g5-C5H5)(PPh3)2RuCl (1a) and 140 mg
(0.86 mmol) of NH4PF6 in dichloromethane (20 mL). The
reaction mixture was stirred at 25 °C for 20 h, whereby
the color of the solution changed from orange to deep
red. Afterwards all volatile materials were removed in oil-
pump vacuum and the remaining residue was dissolved in
dichloromethane and filtered through a pad of Celite.
Removal of the solvent under reduced pressure gave 3a
as a dark red solid which was re-dissolved in tetrahydrofu-
ran (30 mL). Afterwards 1,8-diazabicyclo[5.4.0]undec-7-
ene (DBU, 0.15 mL, 1.0 mmol) was added dropwise,
resulting in a color change from red to yellow. Stirring
was continued for 1 h at 25 °C and all volatiles were
removed under reduced pressure. The residue was
chromatographed under nitrogen on silica gel. Eluting with
tetrahydrofuran/n-hexane (1:3, v/v) provided a yellow
band from which 4a could be isolated as a yellow solid.
Yield: 490 mg (0.56 mmol, 68% based on 1a).
All reactions were carried out under an atmosphere of
purified nitrogen using standard Schlenk techniques. Tetra-
hydrofuran, diethyl ether, petroleum ether and n-hexane
were purified by distillation from sodium/benzophenone
ketyl. Diisopropylamine was dried by distillation from
KOH. Methanol was dried with magnesium and dichloro-
methane was distilled from CaH2. Infrared spectra were
recorded with a Perkin–Elmer FT-IR 1000 spectrometer.
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 (d = 0.00 ppm) with the
solvent as the reference signal (CDCl3: 1H NMR,
d = 7.26; 13C{1H} NMR, d = 77.16) [25]. 31P{1H} NMR
spectra were recorded at 101.255 MHz in CDCl3 with
P(OMe)3 as the external standard (d = 139.0, rel. to
H3PO4 (85%) with d = 0.00 ppm). ESI-TOF mass spectra
were recorded using a Mariner biospectrometry worksta-
tion 4.0 (Applied Biosystems). Cyclic voltammograms were
recorded in a dried cell purged with purified argon at 25 °C.
Platinum wires served as the working electrode and the
counter electrode. A saturated calomel electrode served as
the reference electrode. For the ease of comparison, all
potentials are converted using the redox potential of the fer-
rocene–ferrocenium couple Cp2Fe/Cp2Fe+ (Cp2Fe = (g5-
C5H5)2Fe) as the reference (E0 = 0.00 V) [23]. A conversion
of the given data to the standard normal hydrogen electrode
is possible following the suggestion made by Strehlow et al.
[24]. Electrolyte solutions were prepared from freshly dis-
tilled dichloromethane solutions and [n-Bu4N]PF6
(c = 0.1 M). The appropriate organometallic complexes
were added at c = 1 mM. Cyclic voltammograms were
recorded at a scan rate of 100 mV sꢀ1 using a Radiometer
Copenhagen DEA 101 Digital Electrochemical analyzer
with an IMT 102 Electrochemical Interface. Melting points
were determined using sealed nitrogen purged capillaries on
a Gallenkamp MFB 595 010 M melting point apparatus.
Microanalyses were performed with a CHN-analyzer
3a: IR (KBr, cmꢀ1): 2038m (mC„C), 1624m (mC@C), 842s
(mP–F). 31P{1H} NMR (CDCl3): [d] 49.1 (s, PPh3), 39.2 (s,
1
PPh3), ꢀ145.1 (septet, JPF = 713 Hz).
4a: M.p.: >185 °C (decomp.). IR (KBr, cmꢀ1): 2070s
1
(mC„C). H NMR (CDCl3): [d] 4.36 (s, 5H, C5H5), 7.05–
7.25 (m, 19H, C6H5 + H50/bipy), 7.37–7.50 (m, 13H,
3
3
0
0
0
0
C6H5 + H4/bipy), 7.77 (ddd, JH4 H3 ¼ JH4 H5 ¼ 7:8 Hz,
3
JH4 H6 ¼ 1:8 Hz, 1H, H40/bipy), 8.15 (dd, JH3H4
=
4
0
0
5
8.4 Hz, JH3H6 = 0.8 Hz, 1H, H3/bipy), 8.32 (ddd,
3
4
5
0
0
0
4
0
0
0
JH3 H4 ¼ 7:8 Hz, JH3 H5 ¼ 1 Hz, JH3 H6 ¼ 1 Hz, 1H,
5
H30/bipy), 8.42 (dd, JH6H4 = 2.2 Hz, JH6H3 = 0.8 Hz,
3
0
0
1H,
4
H6/bipy),
8.64
0
(ddd,
JH6 H5 ¼ 4:8 Hz,
JH6 H4 ¼ 1:8 Hz, JH6 H3 ¼ 1 Hz, 1H, H60/bipy). 13C{1H}
NMR (CDCl3): [d] 85.5 (t, JCP = 2 Hz, C5H5), 112.2 (Ci/
bipy), 120.2 (CH/bipy), 120.7 (CH/bipy), 122.7 (CH/bipy),
127.4 (pt, JCP = 4.5 Hz, CH/C6H5), 128.7 (CH/C6H5),
133.9 (pt, JCP = 5 Hz, CH/C6H5), 136.8 (CH/bipy), 137.9
(CH/bipy), 138.7 (dd, JCP = 21.5 Hz, JCP = 20.5 Hz, Ci/
C6H5), 149.1 (CH/bipy), 149.7 (Ci/bipy), 151.2 (CH/bipy),
156.9 (Ci/bipy). 31P{1H} NMR (CDCl3): [d] 49.2 (s, PPh3).
5
0
0
0

R. Packheiser et al. / Journal of Organometallic Chemistry 693 (2008) 933–946
943
Anal. Calc. for C53H42N2P2Ru (869.95): C, 73.17; H, 4.87;
N, 3.22. Found: C, 72.77; H, 4.75; N, 3.09%.
of n-hexane (50 mL) led to the precipitation of the title
compound. After washing the precipitate twice with diethyl
ether (20 mL), complex 10a was obtained as a brown solid.
(Please notice that 10a always contained small amounts of
unreacted 9.)
4.4. Synthesis of (g5-C5H5)(dppf)Ru–C„C–bipy (4b)
1
Complex 4b was synthesized by the same procedure as
described for the synthesis of 4a, except that 1b was used
instead of 1a. Experimental details: (g5-C5H5)(dppf)RuCl
(1b) (250 mg, 0.33 mmol), 5-ethynyl-2,20-bipyridine (2)
(70 mg, 0.39 mmol), NH4PF6 (60 mg, 0.37 mmol), 1,8-
diazabicyclo[5.4.0]undec-7-ene (DBU, 0.1 mL, 0.67 mmol).
Yield: 255 mg (0.28 mmol, 86% based on 1b).
IR (KBr, cmꢀ1): 2208w (mC„CFc), 2078s (mC„CPt). H
3
NMR (CDCl3): [d] 3.24 (s, JHPt = 40 Hz, 12H, NMe2),
4.13 (s, 3JHPt = 41 Hz, 4H, CH2N), 4.21 (pt, JHH = 1.9 Hz,
2H, C5H4), 4.22 (s, 5H, C5H5), 4.46 (pt, JHH = 1.9 Hz, 2H,
3
0
0
C5H4), 7.06 (s, 2H, C6H2), 7.24 (ddd, JH5 H4 ¼ 7:8 Hz,
JH5 H6 ¼ 4:7 Hz, JH5 H3 ¼ 1 Hz, 1H, H50/bipy), 7.74–
3
4
0
0
0
0
3
7.81 (m, 2H, H4,H40/bipy), 8.23 (dd, JH3H4 = 8.4 Hz,
3b: IR (KBr, cmꢀ1): 2037m (mC„C), 1635m (mC@C), 842s
JH3H6 = 0.6 Hz, 1H, H3/bipy), 8.34 (ddd, JH3 H4
¼
5
3
0
0
(mP–F). 31P{1H} NMR (CDCl3): [d] 54.0 (s, dppf), 51.9 (s,
7:8 Hz, JH3 H5 ¼ 1 Hz, JH3 H6 ¼ 1 Hz, 1H, H30/bipy),
4
5
0
0
0
0
1
3
4
5
0
0
0
0
0
0
dppf), ꢀ145.1 (septet, JPF = 713 Hz).
8.65 (ddd, JH6 H5 ¼ 4:7 Hz, JH6 H4 ¼ 1:8 Hz, JH6 H3
¼
1
4
5
4b: M.p.: 193 °C. IR (KBr, cmꢀ1): 2068s (mC„C). H
1 Hz, 1H, H60/bipy), 8.69 (dd, JH6H4 = 2.4 Hz, JH6H3
=
NMR (CDCl3): [d] 3.99 (br s, 2H, C5H4), 4.17 (br s, 2H,
C5H4), 4.32 (br s, 2H, C5H4), 4.35 (s, 5H, C5H5), 5,24 (br
0.6 Hz, 1H, H6/bipy). 13C{1H} NMR (CDCl3): [d] 56.1
(NCH3), 66.2 (Ci/C5H4), 68.7 (CH/C5H4), 70.0 (C5H5),
71.3 (CH/C5H4), 79.7 (NCH2), 86.4 (FcC„C), 87.5
(FcC„C), 105.2 (PtC„C), 118.7 (Ci/C6H2), 120.2 (C3/
bipy), 121.0 (C30/bipy), 122.0 (CH/C6H2), 123.2 (C50/bipy),
125.7 (C5/bipy), 136.9 (C40/bipy), 139.1 (C4/bipy), 143.4
(PtC„C), 146.2 (Ci/C6H2), 149.2 (C60/bipy), 151.6 (C2/
bipy), 152.2 (C6/bipy), 156.5 (C20/bipy) 167.5 (Ci/C6H2).
MS (ESI-TOF, m/z): 774.4 [M+H]+. Anal. Calc. for
C36H34N4FePt (773.62): C, 55.89; H, 4.43; N, 7.24.
Found: C, 54.37; H, 4.32; N, 7.47%. (Deviations in the
elemental analysis are attributed to small amounts of 9
(vide supra)).
3
3
0
0
0
0
s, 2H, C5H4), 7.22 (ddd, JH5 H4 ¼ 7:5 Hz, JH5 H6
¼
4:8 Hz, JH5 H3 ¼ 1 Hz, 1H, H50/bipy), 7.28–7.45 (m,
4
0
0
13H, C6H5 + H4/bipy), 7.50–7.59 (m, 4H, C6H5), 7.77
3
3
4
0
0
0
0
0
0
(ddd, JH4 H3 ¼ JH4 H5 ¼ 7:5Hz, JH4 H6 ¼ 1:8 Hz, 1H,
H40/bipy), 7.81–7.90 (m, 4H, C6H5), 8.22 (dd,
3JH3H4 = 8.4 Hz, JH3H6 = 0.8 Hz, 1H, H3/bipy), 8.33
5
3
4
5
0
0
0
0
0
0
(ddd, JH3 H4 ¼ 7:5 Hz, JH3 H5 ¼ 1 Hz, JH3 H6 ¼ 1 Hz,
1H, H30/bipy), 8.53 (dd, 4JH6H4 = 2.2 Hz, 5JH6H3 = 0.8 Hz,
3
4
0
0
0
0
1H, H6/bipy), 8.65 (ddd, JH6 H5 ¼ 4:8 Hz, JH6 H4
¼
1:8 Hz, JH6 H3 ¼ 1 Hz, 1H, H60/bipy). 13C{1H} NMR
(CDCl3): [d] 68.1 (pt, JCP = 2.4 Hz, CH/C5H4), 71.4 (pt,
JCP = 3 Hz, CH/C5H4), 73.2 (pt, JCP = 2 Hz, CH/C5H4),
76.4 (pt, JCP = 5 Hz, CH/C5H4), 84.9 (t, JCP = 2.4 Hz,
C5H5), 88.6 (dd, JCP = 24.5 Hz, JCP = 23.5 Hz, Ci/C5H4),
110.5 (Ci/bipy), 120.8 (CH/bipy), 121.0 (CH/bipy), 127.3
(pt, JCP = 4.8 Hz, CH/C6H5), 127.4 (pt, JCP = 4.8 Hz,
CH/C6H5), 128.9 (CH/C6H5), 129.3 (CH/C6H5), 133.9
(pt, JCP = 5.8 Hz, CH/C6H5), 134.2 (pt, JCP = 5.8 Hz,
CH/C6H5), 136.8 (CH/bipy), 138.1 (CH/bipy), 140.8 (dd,
JCP = 21.5 Hz, JCP = 20.5 Hz, Ci/C6H5), 141.8 (dd,
JCP = 23.5 Hz, JCP = 22.5 Hz, Ci/C6H5), 149.5 (CH/bipy),
150.1 (Ci/bipy), 151.6 (CH/bipy), 157.1 (Ci/bipy).
31P{1H} NMR (CDCl3): [d] 54.0 (s, PPh2). Anal. Calc.
for C51H40N2P2FeRu (899.76): C, 68.08; H, 4.48; N, 3.11.
Found: C, 67.35; H, 4.69; N, 3.01%.
5
0
0
4.6. Synthesis of Fc–C„C–NCNPt–C„C–py (10b)
Experimental conditions and work-up were identical to
those used in the synthesis of 10a. Experimental details:
Fc–C„C–NCNPtCl (9) (150 mg, 0.24 mmol), 4-ethynyl
n
pyridine (40 mg, 0.39 mmol), BuLi (0.22 mL, 0.35 mmol,
1.6 M in n-hexane). Yield: 75 mg (0.11 mmol, 45%).
M.p.: >195 °C (decomp.). IR (KBr, cmꢀ1): 2212w
1
(mC„CFc), 2077s (mC„CPt). H NMR (CDCl3): [d] 3.20 (s,
3
3JHPt = 42 Hz, 12H, NMe2), 4.12 (s, JHPt = 43 Hz, 4H,
CH2N), 4.21 (pt, JHH = 1.9 Hz, 2H, C5H4), 4.22 (s, 5H,
C5H5), 4.45 (pt, JHH = 1.9 Hz, 2H, C5H4), 7.05 (s, 2H,
C6H2), 7.19–7.23 (m, 2H, C5H4N), 8.37–8.40 (m, 2H,
C5H4N). 13C{1H} NMR (CDCl3): [d] 56.1 (NCH3), 66.2
(Ci/C5H4), 68.7 (CH/C5H4), 70.0 (C5H5), 71.3 (CH/
C5H4), 79.7 (NCH2), 86.4 (FcC„C), 87.4 (FcC„C),
106.4 (PtC„C), 118.9 (Ci/C6H2), 122.1 (CH/C6H2), 126.2
(CH/C5H4N), 136.5 (Ci/C5H4N), 145.4 (PtC„C), 146.2
(Ci/C6H2), 149.3 (CH/C5H4N), 167.3 (Ci/C6H2). MS
(ESI-TOF, m/z): 697.3 [M+H]+. Anal. Calc. for
C31H31N3FePt.1/5CH2Cl2 (713.52): C, 52.52; H, 4.44; N,
5.89. Found: C, 52.76; H, 4.46; N, 5.76%.
4.5. Synthesis of Fc–C„C–NCNPt–C„C–bipy (10a)
To a cooled (ꢀ78 °C) diethyl ether solution containing
65 mg (0.36 mmol) of 5-ethynyl-2,20-bipyridine (2a) was
added 0.22 mL (0.35 mmol) of n-BuLi (1.6 M in n-hexane).
The resulting violet solution was stirred for 30 min at this
temperature and then Fc–C„C–NCNPtCl (9) (150 mg,
0.24 mmol) was added in a single portion. The reaction
mixture was allowed to warm to 25 °C and stirring was
continued for 16 h. All volatile materials were then evapo-
rated in oil-pump vacuum and the residue was re-dissolved
in dichloromethane and filtered through a pad of Celite.
The solution was concentrated to 3 mL and the addition
4.7. Synthesis of Fc–C„C–NCNPt–C„C–py–[Ru] (12)
To 30 mg (0.04 mmol) of [Ru]N„N[Ru] (11) in 15 mL
of dichloromethane were added 55 mg (0.08 mmol) of

944
R. Packheiser et al. / Journal of Organometallic Chemistry 693 (2008) 933–946
Fc–C„C–NCNPt–C„C–py (10b) in a single portion. The
reaction solution was stirred for 3 h at 25 °C, whereby the
color of the solution changed from orange to deep red. The
solvent was concentrated to 3 mL and the product was pre-
cipitated by the addition of 20 mL of n-hexane, washed
twice with 10 mL portions of diethyl ether and dried in
oil-pump vacuum. Complex 7 was obtained as a red solid.
Yield: 70 mg (0.07 mmol, 82% based on 11).
Anal. Calc. for C54H40N2O3BrP2MnRu (1118.63): C,
57.98; H, 3.60; N, 2.50. Found: C, 57.93; H, 3.84; N, 2.40%.
4.10. Synthesis of [(g5-C5H5)(PPh3)2Ru–C„C–
bipy{[Ti](l–r,p-C„CSiMe3)2}Cu]BF4 (17a)
[{[Ti](l–r,p-C„CSiMe3)2}Cu(N„CMe)]BF4
(15b)
(85 mg, 0.12 mmol) was dissolved in 30 mL of tetrahydrofu-
ran and 4a (100 mg, 0.115 mmol) was added in a single por-
tion. After 3 h of stirring at 25 °C the color of the reaction
solution was red. The solution was filtered through a pad
of Celite and all volatiles were removed in oil-pump vacuum.
The remaining red solid was washed twice with 15 mL por-
tions of n-hexane and was afterwards dried in oil-pump vac-
uum. Yield: 140 mg (0.091 mmol, 76% based on 15b).
M.p.: >185 °C (decomp.). IR (KBr, cmꢀ1): 2044s
M.p.: >145 °C (decomp.). IR (KBr, cmꢀ1): 2211w
1
(mC„CFc), 2077s (mC„CPt). H NMR (CDCl3): [d] 2.36 (s,
3
12H, NMe2), 3.23 (s, JHPt = 41 Hz, 12H, NMe2), 4.02 (s,
3
4H, CH2N), 4.13 (s, JHPt = 42 Hz, 4H, CH2N), 4.21 (pt,
JHH = 1.9 Hz, 2H, C5H4), 4.22 (s, 5H, C5H5), 4.46 (pt,
JHH = 1.9 Hz, 2H, C5H4), 7.06 (s, 2H, C6H2), 7.14 (d,
3JHH = 7.9 Hz, 2H, C5H3N), 7.26–7.31 (m, 2H, C5H4N),
3
7.36 (t, JHH = 7.9 Hz, 1H, C5H3N), 9.38–9.43 (m, 2H,
C5H4N). MS (ESI-TOF, m/z): 1062.4 [M+H]+. Anal. Calc.
for C42H50N6Cl2FePtRu (1061.8): C, 47.51; H, 4.75; N,
7.92. Found: C, 47.41; H, 4.81; N, 7.39%.
(mRuC„C), 1923w (mTiC„C). H NMR (CDCl3): [d] ꢀ0.46
1
(s, 18H, SiMe3), 0.22 (s, 9H, SiMe3), 0.29 (s, 9H, SiMe3),
4.37 (s, 5H, C5H5), 6.21 (br s, 4H, C5H4), 6.26 (br s, 4H,
C5H4), 7.04–7.25 (m, 18H, C6H5), 7.35–7.45 (m, 12H,
4.8. Synthesis of (g5-C5H5)(PPh3)2Ru–C„C–
bipy[Mn(CO)3Br] (14a)
C6H5), 7.50 (dd, JH4H3 = 8.5 Hz, JH4H6 = 2 Hz, 1H,
3
4
3
3
0
0
0
0
H4/bipy), 7.56 (dd, JH5 H4 ¼ 7:5 Hz, JH5 H6 ¼ 5 Hz, 1H,
H50/bipy), 8.10–8.21 (m, 3H, H3,H40,H6/bipy), 8.39 (d,
3
3
JH3 H4 ¼ 8 Hz, 1H, H30/bipy), 8.44 (d, JH6 H5 ¼ 5 Hz,
0
0
0
0
Mn(CO)5Br (13) (25 mg, 0.091 mmol) and 4a (75 mg,
0.086 mmol) were dissolved in 20 mL of ethanol and the
reaction solution was heated to reflux for 30 min, whereby
the color changed from orange to dark red. After cooling
the reaction solution to 25 °C the solvent was reduced in
volume to 5 mL, and 15 mL of diethyl ether were added.
On cooling the resulting solution to ꢀ30 °C complex 14a
precipitated. The obtained solid material was washed twice
with 10 mL portions of diethyl ether and dried in oil-pump
vacuum. Complex 14a was obtained as a red-brown solid.
Yield: 60 mg (0.055 mmol, 64% based on 4a).
1H, H60/bipy). 31P{1H} NMR (CDCl3): [d] 49.0 (s,
PPh3). 11B{1H} NMR (CDCl3): [d] 2.4 (BF4). Anal. Calc.
for C79H86N2P2BF4Si4CuRuTi (1537.14): C, 61.73; H,
5.64; N, 1.82. Found: 61.42; H, 5.77; N, 1.64%.
4.11. Synthesis of [(g5-C5H5)(dppf)Ru–C„C–
bipy{[Ti](l–r,p-C„CSiMe3)2}Cu]PF6 (17b)
Experimental conditions and work-up were identical to
those for 17a. Experimental details: [{[Ti](l–r,
p-C„CSiMe3)2}Cu(N„CMe)]PF6 (15a) (55 mg, 0.07 mmol),
4b (65 mg, 0.07 mmol). Yield: 95 mg (0.058 mmol, 84% based
on 15a).
M.p.: >207 °C (decomp.). IR (KBr, cmꢀ1): 2039s
1
(mC„C), 2018s 1927s 1912s (mCO). H NMR (CDCl3): [d]
4.41 (s, 5H, C5H5), 7.08–7.46 (m, 31H, C6H5 + H50/bipy),
7.60–8.06 (m, 4H, H3,H30,H4,H40/bipy), 8.86 (br s, 1H,
H6/bipy), 9.16 (br s, 1H, H60/bipy). 31P{1H} NMR
(CDCl3): [d] 49.0 (s, PPh3). Anal. Calc. for
C56H42N2O3BrP2MnRu (1088.82): C, 61.77; H, 3.89; N,
2.57. Found: C, 61.46; H, 3.93; N, 2.57%.
M.p.: >175 °C (decomp.). IR (KBr, cmꢀ1): 2044s
1
(mRuC„C), 1924w (mTiC„C). H NMR (CDCl3): [d] ꢀ0.44
(s, 18H, SiMe3), 0.22 (s, 9H, SiMe3), 0.29 (s, 9H, SiMe3),
4.03 (br s, 2H, C5H4/Fc), 4.10 (br s, 2H, C5H4/Fc), 4.36
(br s, 2H, C5H4/Fc), 4.37 (s, 5H, C5H5), 5.02 (br s, 2H,
C5H4/Fc), 6.17–6.30 (m, 8H, C5H4/[Ti]), 7.23–7.59 (m,
4.9. Synthesis of (g5-C5H5)(dppf)Ru–C„C–
bipy[Mn(CO)3Br] (14b)
17H, C6H5 + H50/bipy), 7.63 (dd, JH4H3 = 8.5 Hz,
3
4JH4H6 = 2 Hz, 1H, H4/bipy), 7.73–7.83 (m, 4H, C6H5),
3
8.12–8.25 (m, 3H, H3,H40,H6/bipy), 8.38 (d, JH3 H4
¼
0
0
3
7:5 Hz, 1H, H30/bipy), 8.45 (d, JH6 H5 ¼ 4:8 Hz, 1H,
0
0
Complex 14b was synthesized as described earlier for
14a, except that 1b was used instead of 1a. Experimental
details: Mn(CO)5Br (13) (25 mg, 0.091 mmol), 4b (75 mg,
0.083 mmol). Yield: 55 mg (0.045 mmol, 54% based on 4b).
M.p.: >218 °C (decomp.). IR (KBr, cmꢀ1): 2040s
H60/bipy). 31P{1H} NMR (CDCl3): [d] 54.1 (s, PPh2),
1
ꢀ145.1 (septet, JPF = 712 Hz, PF6). Anal. Calc. for
C77H84N2P3F6Si4CuFeRuTi (1625.11): C, 56.91; H, 5.21;
N, 1.72. Found: C, 56.95; H, 5.61; N, 1.71%.
1
(mC„C), 2019s 1929s 1912s (mCO). H NMR (CDCl3): [d]
4.05 (br s, 2H, C5H4), 4.30 (br s, 2H, C5H4), 4.35 (br s,
2H, C5H4), 4.38 (s, 5H, C5H5), 5.13 (br s, 2H, C5H4),
7.26–7.60 (m, 19H, C6H5 + bipy), 7.73–7.87 (m, 6H,
C6H5 + bipy), 8.96 (br s, 1H, H6/bipy), 9.18 (br s, 1H,
H60/bipy). 31P{1H} NMR (CDCl3): [d] 53.9 (s, PPh2).
4.12. Synthesis of [(g5-C5H5)(PPh3)2Ru–C„C–
bipy{[Ti](l–r,p-C„CSiMe3)2}Ag]ClO4 (18a)
{[Ti](l–r,p-C„CSiMe3)2}AgOClO3
(16)
(70 mg,
0.098 mmol) was dissolved in 30 mL of tetrahydrofuran

R. Packheiser et al. / Journal of Organometallic Chemistry 693 (2008) 933–946
945
and 4a (90 mg, 0.104 mmol) was added in a single por-
6. Supplementary material
tion. After 2 h of stirring at 25 °C the color of the reac-
tion solution was red. The solution was filtered through a
pad of Celite and all volatiles were removed in oil-pump
vacuum. The remaining red solid was washed twice with
15 mL portions of n-hexane and was finally dried in oil-
pump vacuum. Yield: 115 mg (0.072 mmol, 74% based on
16).
CCDC 655114, 655116, 659169 and 655115 contain the
supplementary crystallographic data for 4b, 10b, 12 and
17b. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.ca-
m.ac.uk/data_request/cif.
M.p.: >150 °C (decomp.). IR (KBr, cmꢀ1): 2045s
Acknowledgements
1
(mRuC„C), 1955w (mTiC„C). H NMR (CDCl3): [d] ꢀ0.28
(s, 18H, SiMe3), 0.27 (s, 18H, SiMe3), 4.37 (s, 5H,
C5H5), 6.41 (br s, 4H, C5H4), 6.46 (br s, 4H, C5H4),
7.04–7.25 (m, 18H, C6H5), 7.38–7.45 (m, 14H, C6H5),
7.46–7.56 (m, 2H, H4,H50/bipy), 8.01–8.13 (m, 2H,
We are grateful to the Deutsche Forschungsgemein-
schaft (DFG) and the Fonds der Chemischen Industrie
(FCI) for financial support.
H3,H40/bipy), 8.19–8.27 (m, 2H, H30,H6/bipy), 8.53 (d,
JH6 H5 ¼ 4:5 Hz, 1H, H60/bipy). 31P{1H} NMR (CDCl3):
[d] 49.1 (s, PPh3). Anal. Calc. for C79H86O4N2P2ClSi4-
AgRuTi (1594.12): C, 59.52; H, 5.44; N, 1.76. Found:
C, 59.33; H, 5.81; N, 1.67%.
3
0
0
References
[1] For example see (a) V. Balzani, A. Juris, M. Venturi, S. Campagna,
S. Serroni, Chem. Rev. 96 (1996) 759;
(b) V. Balzani, S. Campagna, G. Denti, A. Juris, S. Serroni, M.
Venturi, Acc. Chem. Res. 31 (1998) 26;
(c) C.E. Powell, M.G. Humphrey, Coord. Chem. Rev. 248 (2004)
725;
(d) N.J. Long, C.K. Williams, Angew. Chem., Int. Ed. 42 (2003)
2586;
(e) F. Paul, C. Lapinte, Coord. Chem. Rev. 178–180 (1998) 431;
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4.13. Synthesis of [(g5-C5H5)(dppf)Ru–C„C–
bipy{[Ti](l–r,p-C„CSiMe3)2}Ag]ClO4 (18b)
Experimental conditions and work-up were identical to
those for 18a. Experimental details: {[Ti](l–r,p-C„CSi-
Me3)2}AgOClO3 (16) (45 mg, 0.063 mmol), 4b (60 mg,
0.067 mmol). Yield: 80 mg (0.049 mmol, 78% based on
16).
(g) K.M.C. Wong, S.C.F. Lam, C.C. Ko, N. Zhu, V.W.W. Yam, S.
´
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M.p.: >153 °C (decomp.). IR (KBr, cmꢀ1): 2043s
1
(mRuC„C), 1954w (mTiC„C). H NMR (CDCl3): [d] ꢀ0.27
(s, 18H, SiMe3), 0.27 (s, 18H, SiMe3), 4.04 (br s, 2H,
C5H4/Fc), 4.13 (br s, 2H, C5H4/Fc), 4.36 (s, 5H, C5H5),
4.37 (br s, 2H, C5H4/Fc), 5.07 (br s, 2H, C5H4/Fc), 6.41–
6.48 (m, 8H, C5H4/[Ti]), 7.26–7.56 (m, 17H, C6H5 + H50/
3
4
bipy), 7.61 (dd, JH4H3 = 8.5 Hz, JH4H6 = 2 Hz, 1H, H4/
bipy), 7.74–7.84 (m, 4H, C6H5), 8.06–8.14 (m, 2H,
H3,H40/bipy), 8.23–8.29 (m, 2H, H30,H6/bipy), 8.54 (d,
JH6 H5 ¼ 4:5 Hz, 1H, H60/bipy). 31P{1H} NMR (CDCl3):
3
0
0
(n) G. Vives, A. Carella, J.P. Launay, G. Rapenne, Chem.
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[d]
53.9
(s,
PPh2).
Anal.
Calc.
for
C77H84O4N2P2ClSi4AgFeRuTi (1623.9): C, 56.95; H,
5.21; N, 1.73. Found: C, 56.64; H, 5.20; N, 1.73%.
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