Carbosilane-supported (p-cymene) ruthenium ferrocenyl phosphines in the β-oxopropyl ester synthesis

Article abstract of DOI:10.1016/j.jorganchem.2015.02.036

The synthesis and characterization of a series of carbosilane-supported ferrocenyl phosphine ruthenium complexes of type SiMe_4-n(Fe(η⁵-C₅H₄SiMe₂(CH₂)₃)((η⁵-C₅

Full text of DOI:10.1016/j.jorganchem.2015.02.036

Journal of Organometallic Chemistry 785 (2015) 32e43
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Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Carbosilane-supported (p-cymene) ruthenium ferrocenyl phosphines
in the b-oxopropyl ester synthesis
Claus Schreiner, Janine Jeschke, Bianca Milde, Dieter Schaarschmidt, Heinrich Lang*
€
Technische Universitat Chemnitz, Faculty of Sciences, Institute of Chemistry, Inorganic Chemistry, 09107 Chemnitz, Germany
a r t i c l e i n f o
a b s t r a c t
Article history:
The synthesis and characterization of a series of carbosilane-supported ferrocenyl phosphine ruthenium
complexes of type SiMe4ꢀn(Fe(
h
5-C5H4SiMe2(CH2)3)((
h
5-C5H4PR2)RuCl2(
h
6-p-cymene)))n (p-cymene ¼ 1-
Received 24 November 2014
Received in revised form
17 February 2015
Accepted 23 February 2015
Available online 4 March 2015
i-Pr-4-Me-C6H4; n ¼ 2: 10a, R ¼ Ph; 10b, R ¼ cC6H11; 10c, R ¼ 2-(5-Me)C4H2O); n ¼ 4: 11a, R ¼ Ph; 11b,
R ¼ cC6H11; 11c, R ¼ 2-(5-Me)C4H2O)) is described. For comparative reasons, the non-immobilized fer-
rocenyl phosphine ruthenium complexes [FcPR2(RuCl2(
h
6-p-cymene))] (Fc ¼ Fe(
h h
5-C5H4)( 5-C5H5); 9a,
R ¼ Ph; 9b, R ¼ cC6H11; 9c, R ¼ 2-(5-Me)C4H2O) were prepared. The molecular structure of 9c in the solid
state is reported confirming the expected tetrahedral coordination sphere about the phosphorus atom
and the “piano-stool” geometry about ruthenium. The ruthenium complexes 9e11 are catalytically active
Keywords:
Catalysis
Ferrocenyl phosphines
in the addition of benzoic acid to propargyl alcohol to form b-oxopropyl benzoate. The obtained activities
and productivities show that a good solubility of the catalyst is necessary for a successful catalytic re-
action. Furthermore, the rate of the reaction can be influenced by using less basic and electron-
withdrawing phosphine ligands.
b
-Oxopropyl benzoate
Ruthenium
X-ray structure determination
© 2015 Elsevier B.V. All rights reserved.
Introduction
TPPMS ¼ triphenyl phosphine-m-sulfonate; Fc ¼ Fe(
h -
5-C5H4)(h5
C5H5); R0 ¼ Ph, 2-MeC6H4, cC4H3O, t-Bu, cC6H11) [1,8e11] or dimeric
b-Oxoalkyl esters are important intermediates in organic syn-
ruthenium complexes [Ru(m-O2CH)(CO)2(PPh3)]2 [10] as catalysts. It
thesis, since they can be transformed into heterocyclic furanones or
imidazoles [1‒3] and they can serve as activated esters for peptide
synthesis [4], or as photolabile protecting groups for carboxylic
acids [5]. Numerous synthetic methodologies for the preparation of
was found that phosphines such as PMe3 and PPh3 achieve high
conversions [1]. However, when electron-deficient phosphines
(e.g., P(cC4H3O)3) in combination with [RuCl2( 6-p-cymene)] are
h
used in the related enol ester synthesis a better catalytic perfor-
mance was obtained [12]. Another approach was reported by
b-oxoalkyl esters including the carboxylation of a-halo ketones [5],
0
ꢀ
ꢀ
ꢀ
hydration/esterification of propargylic alcohols [6], or oxidation of
ketones via metal acetate complexes [7] are known. On the other
hand, the ruthenium-catalyzed addition of carboxylic acids to
propargylic alcohols represents an elegant and atom-economic
alternative to classical synthetic methodologies [8], since the
starting materials are easily accessible, various functionalities at the
carboxylic acid as well as at the alkyne are tolerated and the for-
mation of side-products is limited [1,9,10]. The catalytic reaction
proceeds under mild conditions (60 ꢁC, 6 h) [1] and the best results
were obtained by applying mononuclear half-sandwich complexes
Stepnicka et al. who immobilized 1 -(diphenylphosphino)ferrocene
carboxylic acid (¼hdpf) on the mesoporous molecular sieve MCM-
41, which was further reacted with [RuCl2(h
6-p-cymene)]2 to give a
[RuCl2(h
6-p-cymene)(hdpf)]-modified material [13]. However, in
the reaction of benzoic acid with propargyl alcohol the immobi-
lized catalysts showed lower activity and productivity, when
compared to the homogenous catalysts [RuCl2(h
6-p-cyme-
ne)(hdpf)], which is most probably caused by the formation of
polymeric side products [13].
We here report on the synthesis and characterization of
carbosilane-supported ferrocenyl phosphine ruthenium complexes
of type [RuCl2(
h
6-arene)(PR3)] (arene
¼
p-cymene, C6Me6;
PR3
¼
PMe3, PPh3, phosphoramidite, TPPMS, P(C≡CFc)R02;
and their application in the catalytic synthesis of
benzoate. Thereby, the main focus was to clarify whether strong or
weak donating phosphines accelerate the catalytic reaction and to
b-oxopropyl
s
study the effect of the degree of immobilization on the perfor-
mance of the appropriate catalysts.
* Corresponding author. Tel.: þ49 (0)371 531 21210; fax: þ49 (0)371 531 21219.
E-mail address: heinrich.lang@chemie.tu-chemnitz.de (H. Lang).
http://dx.doi.org/10.1016/j.jorganchem.2015.02.036
0022-328X/© 2015 Elsevier B.V. All rights reserved.

C. Schreiner et al. / Journal of Organometallic Chemistry 785 (2015) 32e43
33
Table 1
Synthesis of 6, 7, 10 and 11.
Results and discussion
Yield/%a
Compd.
R
Yield/%b
Synthesis and characterization
Compd.
R
6a
6b
6c
7a
7b
7c
C6H5
71
80
74
62
58
67
10a
10b
10c
11a
11b
11c
C6H5
98
95
96
97
96
95
cC6H11
cC6H11
As starting molecules Fe(
h
5-C5H4PR2)(
h
5-C5H4Br) (3a, R ¼ Ph;
3b, R ¼ cC6H11; 3c, R ¼ 2-(5-Me)C4H2O) were chosen, which were
synthesized by a modified reaction protocol firstly described by
Dong and co-workers (Reaction 1) [14]. Sub-stoichiometric
amounts of n-butyl lithium were used to prevent the formation of
di-substituted phosphines, since it appeared that their separation
using different methodologies is difficult.
2-(5-Me)C4H2O
C6H5
2-(5-Me)C4H2O
C6H5
cC6H11
cC6H11
2-(5-Me)C4H2O
2-(5-Me)C4H2O
a
Based on 5a and 5b, respectively.
Based on 3aec.
b
All compounds were characterized by elemental analysis
(except 6 and 7, vide supra), IR and NMR (1H, 13C{1H}, 29Si{1H}, 31P
{1H}) spectroscopy. In addition, the structure of 9c in the solid state
was determined by single crystal X-ray structure analysis.
The IR spectra of the sulfides 6a-Se6c-S and 7a-Se7c-S and the
ruthenium complexes 10aec and 11aec exhibit several character-
istic absorptions for the carbosilane backbone, e.g. the SieC defor-
mation vibration (
stretching vibrations (
y
~ z 1250 cmꢀ1) as well as the SieC and CeH
y
~ z 830 cmꢀ1 and ~ z 2850e2950 cmꢀ1
y ,
Treatment of 3aec with n-BuLi and the respective chlorosilane
SiMe4ꢀn((CH2)3SiMe2Cl)n (5a, n ¼ 4; 5b, n ¼ 2) gave the two- and
fourfold substituted phosphanylferrocenyl carbosilanes 6aec and
7aec in good yields (Scheme 1, Table 1). Due to their sensitivity
towards oxygen, 6aec and 7aec were converted into the corre-
sponding sulfides 6a-Se6c-S and 7a-Se7c-S for analytical purposes
(elemental analysis and IR spectroscopy) by their reaction with
elemental sulfur.
respectively). In addition, typical P]S absorptions can be observed
for the respective sulfides 6a-Se6c-S and 7a-Se7c-S, which show a
dependency on the electronic nature of the organic group at the
phosphorus atom. With a decreasing ꢀI effect, the P]S stretching
frequencies decrease, i.e. 6a-S, 656 cmꢀ1; 6c-S, 694 cmꢀ1
.
For the characterization of the newly prepared molecules 9e11
NMR spectroscopy is suitable at which 2D methods (HH-gs-COSY,
HSi-gs-HMBC, HC-gs-HSQC, HC-gs-HMBC) are of importance to
confirm the suggested molecular structures.
Ruthenium complexes 10aec and 11aec were accessible by
treatment of 6aec and 7aec with [RuCl2(
h
6-p-cymene)]2 (8) in
The 1H NMR spectra of 3, 6, 7 and 9e11 consist of two signal sets
dichloromethane at ambient temperature (Scheme 1, Table 1). After
appropriate work-up, these complexes could be isolated as air and
moisture stable red solids. In addition, the non-functionalized fer-
rocenyl phosphines 4aec were synthesized and converted into the
respective ruthenium complexes 9aec for comparative purposes
(Scheme 1, Experimental section).
for the
between 3.6 and 4.7 ppm as typical for ferrocenes featuring C5H4
ligands [15]. Especially the signals for the protons are highly
dependent on the electronic nature of the phosphorus-bonded
organic groups as they are shifted to lower field, when electron-
withdrawing groups are attached (e.g., Ha/C5H4P: 6b, 4.12 ppm;
a and b protons of the ferrocenyl cyclopentadienyl moieties
a
Scheme 1. Synthesis of 4, 6, 7 and 9e11 (a, R ¼ C6H5; b, R ¼ cC6H11; c, R ¼ 2-(5-Me)C4H2O). (i) n-BuLi, tetrahydrofuran, ꢀ50 ꢁC, 1 h; (ii) dichloromethane, 25 ꢁC, 2 h.

34
C. Schreiner et al. / Journal of Organometallic Chemistry 785 (2015) 32e43
6c, 4.39 ppm). However, the resonance signals of the carbosilane
backbone with their distinct splitting pattern are not influenced by
the phosphine substituents R. Oxidation of the phosphorus atom, as
given in compounds 6-S and 7-S, respectively, does not influence
the chemical shift of the carbosilane backbone but results in a
downfield shift of ca. 0.3 ppm of the C5H4 a proton signals (e.g., Ha/
C5H4P: 6a, 4.07; 6a-S, 4.42 ppm). The 1H NMR spectra of the
ruthenium complexes 10 and 11 show the expected signal patterns
as typical for the ferrocenyl and carbosilane moieties with chemical
shifts similar to those of the sulfides 6-S and 7-S. In contrast, the
chemical shifts of the p-cymene protons depend on the nature of
the phosphino units. More basic phosphines induce a shift of the
respective protons to a higher magnetic field.
In the 13C{1H} NMR spectra of 6 and 7 a characteristic signal
pattern for the carbosilane backbone can be found between 17 and
22 ppm, independent from the PR2 building blocks. On the other
hand, the internal silicon atom of the SieCH2 unit is by 2.5 ppm
shifted to higher field, when going from 6 to 7. The spectra of the
ferrocenyl C5H4 rings show the expected resonance signals at ca.
1
70 ppm with typical JCP coupling constants of which JCP shows a
Fig. 1. ORTEP diagram (50% probability level) of the molecular structure of 9c with the
atom-numbering scheme. All hydrogen atoms and the packing solvents chloroform
and pentane have been omitted for clarity. Selected bond lengths (Å) and angles (ꢁ):
Ru1eP1 ¼ 2.3326(10), Ru1eCl1 ¼ 2.3965(9), Ru1eCl2 ¼ 2.4110(10), P1eC10 ¼ 1.808(4),
P1eC11 ¼ 1.799(4), P1eC16 ¼ 1.795(4), D1eFe1 ¼ 1.641(3), D2eFe1 ¼ 1.641(3),
direct dependence on the electronic properties of the appropriate
1
phosphine (e.g., JCP ¼ 17 (6b, 7b), 7 (6a, 7a), 5 (6c, 7c) Hz). The
oxidation of phosphorus, as given in compounds 6-S and 7-S, barely
1
influences the shift of the resonance signals, though the JCP
coupling constants are greatly enlarged (e.g., 1JCP ¼ 80 (6b-S, 7b-S),
100 (6a-S, 7a-S), 110 (6c-S, 7c-S) Hz), which is a common phe-
nomenon for phosphorus(V) compounds [16]. A similar behavior is
found for ruthenium complexes 10 and 11. Merely, the shifts of the
ipso-carbon atoms to lower field and the 1JCP coupling constants are
D3eRu1
¼
1.697(2), Cl1eRu1eCl2
91.44(3), C16eP1eRu1
¼
¼
88.26(3), Cl1eRu1eP1
113.78(14), C11eP1eRu1
¼
81.95(3),
112.79(13),
104.19(19),
Cl2eRu1eP1
¼
¼
C10eP1eRu1 ¼ 124.38(14), C10eP1eC11 ¼ 97.63(19), C10eP1eC16
¼
C11eP1eC16
¼
100.56(19), C11eO1eC14
¼
106.9(3), C16eO2eC19
¼
107.8(4),
D1eFe1eD2 ¼ 176.87(5). (D1 denotes the centroid of C5H4 at Fe1, D2 denotes the
centroid of C5H5 at Fe1, D3 denotes the centroid of C6H4 at Ru1).
affected by the coordination of phosphorus to [RuCl2(h
6-p-cym-
ene)]. However, the magnitude of 1JCP is smaller, when compared to
compounds 6-S and 7-S, respectively (e.g., 1JCP ¼ 5 (6c, 7c), 110 (6c-
From Table 2 it can be seen that the most basic phosphine and
S, 7c-S), 55 (10c, 11c) Hz) but is still a measure for the
s donor
hence the strongest
s donor is the cyclohexyl derivative 4b-Se. In
capability of the respective phosphine.
contrast, the methylfuryl-carrying seleno phosphine 4c-Se with a
In addition, the newly prepared compounds have been identi-
fied by 29Si{1H} and 31P{1H} NMR spectroscopy. The 29Si{1H}
spectra show two singlets of which the one at higher magnetic field
can be assigned to the outer silicon atoms. Nevertheless, a shift
upon oxidation or coordination of P to Ru cannot be observed. More
expressive is 31P{1H} NMR spectroscopy. Upon coordination of the
phosphorus atom to ruthenium a significant shift to lower field
takes place, i.e. 6a, ꢀ17.9 ppm; 10a, 18.4 ppm. Oxidation of phos-
phorus also induces, as expected, a significant shift to lower field
(e.g., 6a, ꢀ17.9 ppm; 6a-S, 41.6 ppm). This allows controlling the
reaction progress of 6 and 7 with sulfur or the ruthenium species.
The nature of the organic group bound to the phosphorus atom also
influences the chemical shift (e.g., 6a, ꢀ17.9 ppm; 6b, ꢀ8.6 ppm)
1
significantly higher J31Pe77Se magnitude is less basic. Based on
the obtained data it is obvious that the electronic character of the
phosphine can easily be modified by varying the attached
groups.
The structure of 9c in the solid state was determined by single
crystal X-ray structure analysis (Fig. 1). Suitable crystals were ob-
tained by slow diffusion of pentane into a saturated chloroform
solution containing 9c at ambient temperature. Selected bond
distances (Å) and angles (ꢁ) are given in the caption of Fig. 1. The
crystal and structure refinement data are presented in the
Experimental section.
Complex 9c crystallizes in the triclinic space group P1 and is set-
up by one ferrocenylphosphanyl unit, two 2-(5-methyl)furyl groups
and a ruthenium dichloro p-cymene moiety at the phosphorus
atom. The bond angles at P1 are between 97.63(19) and 104.19(19)ꢁ
confirming the tetrahedral geometry. The ferrocenyl groups exhibit
an almost eclipsed conformation (7.7(3)ꢁ) and the D1eFe1 and
D2eFe1 separations are 1.641(3) and 1.641(3) Å (D1 denotes the
centroid of C5H4 at Fe1, D2 denotes the centroid of C5H5 at Fe1). The
bond angles at Ru1 are between 81.95(3) and 91.44(3) indicating
the typical “piano-stool” geometry. All other structural parameters
are unexceptional and correspond to those of related compounds
[9,11,13].
and hence the electronic properties of the phosphine. The
s donor
capacity of phosphines can be quantified by the coupling constant
1J31Pe77Se of the appropriate seleno phosphines [16,17]. Electron-
1
withdrawing groups at the phosphorus atom increase J31Pe77Se
due to the increased s character of the phosphorus orbital involved
in the PeSe bonding. To verify the basicity of the carbosilane-
functionalized phosphines 6 and 7 the corresponding non-func-
tionalized seleno phosphines 4a-See4c-Se were prepared [16]. The
1
31P{1H} NMR data and the J31Pe77Se coupling constants are sum-
marized in Table 2.
Table 2
1
Chemical shifts and J31Pe77Se data of 4a-See4c-Se.
Catalysis
Compd.
d/ppm
1J31P-77Se/Hz
4a-Se
4b-Se
4c-Se
30.8
48.8
ꢀ7.2
733
699
756
As model reaction, to see if 9e11 can successfully be used as
catalysts, the conversion of benzoic acid with propargyl alcohol to
produce b-oxopropyl benzoate was chosen (Reaction 2).

C. Schreiner et al. / Journal of Organometallic Chemistry 785 (2015) 32e43
35
The reaction conditions were optimized by varying the internal
standard, the solvent and the ruthenium loading. The conversions
were determined by 1H NMR spectroscopy. In contrast to the re-
action conditions reported by Dixneuf [1], initial experiments
showed that the applied catalysts need higher reaction tempera-
tures and hence the catalytic reactions were performed at 80 ꢁC.
1.0 mol-%, respectively, are less significant (e.g., 0.75 mol-%, 70%;
1.0 mol-%, 75% after 24 h). In further catalytic reactions catalyst
loadings of 1.0 mol-% per ruthenium were applied.
Solvent
The success of a homogenous reaction is highly dependent on
the solubility of the respective catalyst in the reaction medium. The
Internal standard
most commonly used solvent in
b-oxoalkyl ester synthesis is
toluene [1,10,20]. Preliminary studies showed that the solubility of
the carbosilane ruthenium complexes in toluene decreases in the
order 9 > 10 > 11 and hence the catalytic activity and productivity
decreases (Table 5, Figure S3, Supporting information). To clarify,
whether the differences in activity and productivity are based on
solubility issues, we compared the conversions for 9c and the
fourfold substituted carbosilane 11c (Table 5, Figure S4, Supporting
information) using catalyst loadings of 0.5 and 1.0 mol-%, respec-
tively. As it can be seen from Table 5 and Figure S4 (Supporting
information) the most significant differences in activity can be
observed for non-supported 9c which achieves conversions of 78
and 87%, when increasing the amount of ruthenium (vide supra). In
contrast, complex 11c shows virtually no dependency on the con-
centration (0.5 mol-%, 38%; 1.0 mol-%, 40%) which is attributed to its
lower solubility in toluene.
An ideal standard contains various beneficial properties such as
inert behavior in the catalytic reaction, low vapor pressure and
separated signals in the 1H NMR spectra. Beletskaya et al. [18]
suggested that acetyl ferrocene is a suitable standard for Suzu-
kieMiyaura and BuchwaldeHartwig cross-couplings. Preliminary
tests applying acetyl ferrocene showed that the activities and
productivities were lower, when compared to acenaphthene as
internal standard (Table 3, Figure S1, Supporting information). This
result can most probably be attributed to a competitive reaction of
the acetyl group with the ruthenium center resulting in a hindering
of the
h
2-coordination of the acetylide group of the propargyl
alcohol. However, after 24 h almost identical conversions (e.g., 9c,
94 and 95%, respectively; Table 3) were achieved, which suggests
that the coordination of the acetyl ferrocene is a reversible reaction.
Although, acenaphthene has a relatively low vapor pressure (0.3 Pa,
25 ꢁC [19]) it is preferable over acetyl ferrocene as internal standard
due to the aforementioned activity problems and its significantly
lower toxicity.
Since the newly synthesized catalysts exhibit a divergent solu-
bility behavior, which depends on the nature of the organic groups
attached to the phosphorus atom as well as the degree of immo-
bilization, we decided to use different reaction media to prevent
Ruthenium loading
Table 4
Dependency of the productivity on the Ru loading.
b-Oxoalkyl ester synthesis is usually performed using a ruthe-
nium loading of 1.0 mol-% [1,10,11,20]. Since systematic studies
concerning the influence of the catalyst concentration on the ach-
ieved conversions are not described so far, we decided to apply the
Ru loading/mol-%
Conversion/%
3 h
6 h
9 h
24 h
0.25
0.5
0.75
1.0
2
4
8
7
18
27
29
20
33
48
54
39
60
70
75
well-known catalyst [RuCl2(PPh3)(
mation of -oxopropyl benzoate using ruthenium loadings in the
h
6-p-cymene)] [1] in the for-
b
range of 0.25e1.0 mol-% (Table 4, Figure S2, Supporting
information). From Table 4 and Figure S2 it can be seen that the
higher the catalyst loading, the higher the conversion is. Especially
at low ruthenium loadings of 0.25 mol-% the reaction proceeds very
slowly (e.g., 24 h, 39%). In contrast, the differences of the conver-
sions achieved with a higher ruthenium loading of 0.75 and
10
Reaction conditions: 3.0 mmol benzoic acid, 4.5 mmol propargyl alcohol, 1.5 mmol
acenaphthene, 15 mL toluene, 1.0 mol-% [RuCl2(PPh3)(h6-p-cymene)], 80 ꢁC.
Table 5
Activity and productivity of 9b, 10b and 11b after 9 h and of 9c and 11c with
ruthenium loadings of 0.5 and 1.0 mol-%.
Table 3
Compd.
TON
TOF/hꢀ1
Dependency of the productivity on the applied internal standard.
9b
9c
66a
94a
78b
39b
29a
40a
38b
7a
7a,c
4b,c
4a
Compd.
Acetyl ferrocene
Conversiona/%
Acenaphthene
Conversiona/%
Conversionb/%
Conversionb/%
10b
11b
11c
9a
9b
9c
24
38
30
82
88
95
23.5
55
40
79
87
94
3a
3a,c
2b,c
Reaction conditions: 3.0 mmol benzoic acid, 4.5 mmol propargyl alcohol, 0.75 mmol
acetyl ferrocene or 1.5 mmol acenaphthene, 15 mL toluene, 1.0 mol-% based on Ru,
80 ꢁC.
Reaction conditions: 3.0 mmol benzoic acid, 4.5 mmol propargyl alcohol,
1.5 mmol acenaphthene, 15 mL toluene, 80 ꢁC.
a
1.0 mol-% based on Ru.
0.5 mol-% based on Ru.
a
b
Reaction time 7.5 h.
b
c
Reaction time 24 h.
TOFs between 3 and 9 h.

36
C. Schreiner et al. / Journal of Organometallic Chemistry 785 (2015) 32e43
Table 6
Table 7
Influence of the solvent on the obtained conversions.
Productivity of complexes 11aec after 24 h and a ruthenium loading of 0.1 mol-%.
Solvent
Conversion/%
4 h
Compd.
Conversion/%
TON
7 h
24 h
11a
11b
11c
39
30
48
390
300
480
1,4-Dioxane
Toluene
Toluene/MeCN
Chlorobenzene
4
7
26
45
7
16.5
47
22
78
82
85
Reaction conditions: 3.0 mmol benzoic acid, 4.5 mmol propargyl alcohol, 1.5 mmol
acenaphthene, 15 mL chlorobenzene, 0.1 mol-% 11a e c (based on Ru), 80 ꢁC.
69
Reaction conditions: 3.0 mmol benzoic acid, 4.5 mmol propargyl alcohol, 1.5 mmol
acenaphthene, 15 mL solvent, 1.0 mol-% 9c, 80 ꢁC.
To investigate the influence of the basicity of the respective
phosphine on the productivity of the catalyst, we reduced the
catalyst loading to 0.1 mol-% (based on Ru). The conversions ob-
tained for 11aec are shown in Table 7. The results indicate that
phosphine complex 11c, bearing electron-withdrawing methylfuryl
groups, is the most productive system (48%, TON: 480). In contrast,
electron-rich 11b shows visibly lower conversions of 30% (TON:
300) attributing to its lower stability in solution, which is prob-
lematic when long reaction times and low catalyst loadings are
required.
In contrast to the productivities, the activities show obvious
tendencies concerning basicity even with higher catalyst loadings
of 1.0 mol-% (Table 8, Figure S6, Supporting information). From
Table 8 and Figure S6 it is obvious that the methylfuryl-substituted
carbosilane-supported compounds 10c and 11c and the non-sup-
ported ruthenium complex 9c with their electron-withdrawing
methylfuryl groups are noticeably more active, when compared
solubility problems. We examined more polar solvents such as 1,4-
dioxane, chlorobenzene and a mixture of toluene/acetonitrile (ratio
10:1, v/v). As catalyst, the non-supported complex [P(2-(5-Me)
C4H2O)2(Fc)RuCl2(h
6-p-cymene)] (9c) was applied, which is soluble
in all tested solvents and hence the obtained conversions should
only dependent on the solvent itself. As it can be seen from Table 6
and Figure S5 (Supporting information), the catalytic reaction
proceeds slowly in toluene and 1,4-dioxane with conversions below
20% after 7 h. The conversion obtained in toluene (78%) after 24 h is
considerably higher, when compared to 1,4-dioxane (22%) (Table 6,
Figure S5, Supporting information). Addition of 10 vol-% of aceto-
nitrile barely increases the productivity (82%), whereas the rate of
the reaction is significantly increased with conversions of 47% after
7 h (toluene: 16.5%). However, the highest activity and productivity
is obtained, when chlorobenzene was used as solvent (70% con-
version after 7 h). For this reason, this solvent was used in further
catalytic reactions.
to strong (9be11b) and moderate (9ae11a)
s donating ferrocenyl
phosphines.
The obtained activities and conversions show that a good sol-
ubility of the applied catalyst is mandatory for the success of the
oxopropyl ester synthesis. In case of incomplete solubility of the
catalyst a great loss of activity is to be expected. Furthermore, we
b
-
Catalyst screening
All ruthenium complexes 9e11 were studied under optimized
reaction conditions in the addition of benzoic acid to propargyl
observed that the catalytic formation of
b-oxopropyl esters is
intolerant regarding immobilization unless the support is
completely soluble in the reaction medium. In terms of basicity, the
applied catalyst systems should carry electron-withdrawing and
less basic groups to enhance the rate of the reaction which is in
agreement with the results published earlier by Goossen and co-
workers [12].
alcohol to give b-oxopropyl benzoate (1.0 mol-% Ru loading, chlo-
robenzene as solvent and acenaphthene as internal standard). In
Fig. 2 the reaction profiles obtained for cyclohexyl-substituted
complexes 9b, 10b and 11b are depicted. It can be seen that the
degree of immobilization has virtually no influence on the catalytic
performance due to the good solubility of the catalyst in the solvent
chlorobenzene. Turnover frequencies of 7e8 hꢀ1 and conversions
ꢂ90% can be achieved for all catalysts 9e11 after 24 h. Furthermore,
these results show that the influence of the basicity of the
respective phosphine ligands on the productivity is negligible un-
der these reaction conditions.
Conclusion
Within this study the synthesis and characterization of a series
of carbosilane-supported ferrocenyl phosphine ruthenium com-
plexes of type SiMe4ꢀn((h h
5-C5H4SiMe2(CH2)3)Fe( 5-C5H4PR2)
RuCl2(
h
6-p-cymene))n (p-cymene ¼ 1-i-Pr-4-Me-C6H4; n ¼ 2, 4:
80
70
60
50
40
30
R ¼ Ph, cC6H11, 2-(5-Me)C4H2O) is reported. The carbosilane-
supported ruthenium complexes were used as catalysts in the
formation of b-oxopropyl benzoate by addition of benzoic acid to
propargyl alcohol. The reaction conditions were optimized
including the ruthenium loading (1.0 mol-%), the temperature
(80 ꢁC), the solvent (chlorobenzene) and the internal standard
(acenaphthene). All complexes are suitable as catalysts although
their performance is highly dependent on the solubility, due to the
20
9b
Table 8
10
0
11b
10b
Activity of complexes 9e11 after 9 h.
Compd.
TOF/hꢀ1
Compd.
TOF/hꢀ1
Compd.
TOF/hꢀ1
0
100
200
300
400
500
600
9a
9b
9c
7
8
10
10a
10b
10c
6.5
7
9
11a
11b
11c
6
7.5
9
t
/ min
Fig. 2. Reaction profile for the coupling of benzoic acid (3.0 mmol) with propargyl
alcohol (4.5 mmol) using 1.0 mol-% of 9b, 10b and 11b (based on Ru) in chlorobenzene
(15 mL) at 80 ꢁC.
Reaction conditions: 3.0 mmol benzoic acid, 4.5 mmol propargyl alcohol, 1.5 mmol
acenaphthene, 15 mL chlorobenzene, 1.0 mol-% 9e11 (based on Ru), 80 ꢁC.

C. Schreiner et al. / Journal of Organometallic Chemistry 785 (2015) 32e43
37
low tolerance of the reaction regarding immobilization. However,
the degree of immobilization does not influence the activity or
productivity. In accordance to the results published by Goossen
et al. [12], catalysts featuring less basic electron-withdrawing
groups enhance the rate of the reaction.
(ddq, 3JPH ¼ 1.9 Hz, 3JHH ¼ 3.1 Hz, 5JHH ¼ 0.2 Hz, 2H, H3/5-MeC4H2O).
13C{1H} NMR (125.81 MHz, CDCl3, ): 14.1 (s, CH3), 68.5 (s, Cb/
d
C5H4Br), 71.2 (s, Ca/C5H4Br), 74.0 (d, 3JCP ¼ 5 Hz, Cb/C5H4P), 75.5 (d,
2
1JCP ¼ 3 Hz, Ci/C5H4P), 75.8 (d, JCP ¼ 18 Hz, Ca/C5H4P), 77.9 (s, Ci/
C5H4Br), 107.0 (d, 3JCP ¼ 6 Hz, C4/5-MeC4H2O), 121.1 (d, 2JCP ¼ 22 Hz,
1
C3/5-MeC4H2O), 150.2 (d, JCP ¼ 4 Hz, C2/5-MeC4H2O), 156.7 (d,
Experimental
3JCP ¼ 3 Hz, C5/5-MeC4H2O). 31P{1H} NMR (202.5 MHz, CDCl3,
d
): ꢀ66.7 (s). *) The sample included 15% 1-di(2-(5-methylfuryl)
General procedures
phosphanyl)ferrocene (4b) which could not be separated from the
title compound.
All reactions were carried out under an atmosphere of argon
using standard Schlenk techniques. Toluene, tetrahydrofuran and
dichloromethane were purified by distillation from sodium and
sodium/benzophenone; dichloromethane was purified by distilla-
tion from calcium hydride. Column chromatography was carried
Synthesis of Fe(h h
5-C5H4P(2-(5-Me)C4H2O)2Se)( 5-C5H5) (4c-Se)
To a toluene solution of 4c (123 g, 0.27 mmol) selenium (43 mg,
0.55 mmol, 2.0 equiv) was added in a single portion. The reaction
mixture was refluxed for 30 min and after cooling to ambient
temperature the suspension was filtered through a pad of Celite.
After removal of the solvent in oil pump vacuum, the title com-
pound 4c-Se was obtained as an orange solid. Yield: 125 mg
(0.27 mmol, 100% based on 4c). Anal. Calcd. for C20H19FeO2PSe
(457.14 g/mol): C, 52.55; H, 4.19. Found: C, 52.38; H, 4.12; Mp.:
out using silica with a particle size of 40e60
mm (230e400 mesh
(ASTM), Becker) or alumina with a particle size of 90
mm (standard,
Merck KGaA). Celite (purified and annealed, Erg. B.6, Riedel de
Haen) was used for filtrations.
NMR spectra were recorded at 298 K with a Bruker Avance 250
or a Bruker Avance III 500 spectrometer. The 1H NMR spectra were
recorded at 250.13 or 500.3 MHz, the 13C{1H} at 125.7 MHz, the 29Si
{1H} at 49.66 or 99.39 MHz and the 31P{1H} NMR spectra at 101.249
138 ꢁC. IR (NaCl, ~/cmꢀ1): 577 (m, P]Se), 1021 (s, CeOeC), 1590 (m,
y
C]C), 2911/2956 (w, CeH), 3091 (w, ]CeH). 1H NMR (500.30 MHz,
or 202.5 MHz. Chemical shifts are reported in
million) downfield from tetramethylsilane with the solvent as
reference signal (1H NMR: standard internal CDCl3, 7.26; 13C{1H}
NMR: standard internal CDCl3,
77.16; 29Si{1H} NMR: standard
external rel. SiMe4,
0.0; 31P{1H} NMR: standard external rel. 85%
H3PO4, 0.0; P(OMe)3, 139.0). Elemental analyses were carried
d
units (parts per
CDCl3,
d
): 2.32 (s, 6H, CH3), 4.16 (s, 5H, C5H5), 4.45 (dpt, 4JPH ¼ 1.8 Hz,
3/4
J
¼ 1.8 Hz, 2H, Hb/C5H4), 4.67 (dpt, 3JPH ¼ 2.7 Hz, 3/4JHH ¼ 1.8 Hz,
HH
d
2H, Ha/C5H4), 6.04 (ddq, 4JPH ¼ 1.8 Hz, 3JHH ¼ 3.2 Hz, 4JHH ¼ 0.9 Hz,
3
3
d
2H, H4/5-MeC4H2O), 6.88 (ddq, JPH ¼ 3.2 Hz, JHH ¼ 3.2 Hz,
d
5JHH ¼ 0.4 Hz, 2H, H3/5-MeC4H2O). 13C{1H} NMR (125.81 MHz,
d
d
CDCl3,
d
): 14.0 (s, CH3), 70.0 (s, C5H5), 71.6 (d, 3JPC ¼ 11 Hz, Cb/C5H4),
out with a Thermo Flashea 1112 series instrument. Melting points
of analytical pure samples were determined with a Gallenkamp
MFB 595 010 M melting point apparatus. FT IR spectra were
recorded with a Thermo Nicolet IR 200 spectrometer using NaCl
plates. All starting materials were obtained from commercial sup-
pliers and used without further purification. 1,10-Dibromo ferro-
cene (1) [14], P(cC6H11)2Cl (2b) [21], P(2-(5-Me)C4H2O)2Cl (2c) [22],
Me2Si(CH2CH2CH2SiMe2Cl)2 (5a) [23], Si(CH2CH2CH2SiMe2Cl)4 (5b)
71.9 (d, 1JPC ¼ 101 Hz, Ci/C5H4), 72.8 (d, 2JPC ¼ 14 Hz, Ca/C5H4), 107.5
3
2
(d, JPC ¼ 9 Hz, C4/5-MeC4H2O), 123.2 (d, JPC ¼ 21 Hz, C3/5-
MeC4H2O), 144.8 (d, JPC ¼ 117 Hz, C2/5-MeC4H2O), 158.6 (d,
1
3JPC ¼ 7 Hz, C5/5-MeC4H2O). 31P{1H} NMR (101.25 MHz, CDCl3,
d
): ꢀ7.2 (s, 1J77Se31P ¼ 756 Hz).
General procedure for the synthesis of carbosilane-ferrocenyl
phosphines 6aec and 7aec
[24], and [RuCl2(h
6-p-cymene)]2 (8) [25] were prepared according
to published procedures.
To a solution of 2.5 or 5.0 equiv of 3aec dissolved in tetrahy-
drofuran (10 mL/mmol) 2.25 or 4.5 equiv of n-butyl lithium (2.5 M
in hexane) were added dropwise at ꢀ50 ꢁC. After stirring the re-
action mixture for 1 h at ꢀ50 ꢁC, a solution of 5 (1.0 equiv) in
tetrahydrofuran (10 mL/mmol) was dropwise added. The reaction
mixture was stirred for 1 h at ambient temperature and the solvent
was removed in oil pump vacuum. The crude product was purified
by column chromatography on alumina and dried in oil pump
vacuum. For more details see below.
Synthesis of 1-bromo-10-di(2-(5-methylfuryl)phosphanyl)ferrocene
(3c)
To a solution of 1,10-dibromo ferrocene (1, 2.58 g, 7.50 mmol,
1.0 equiv) dissolved in tetrahydrofuran (40 mL) a 2.5 M solution of
n-butyl lithium in hexane (2.85 mL, 7.13 mmol, 0.95 equiv) was
added dropwise at ꢀ70 ꢁC. After stirring the reaction solution at
this temperature for 1 h, chlorodi-2-(5-methyl)furyl phosphine (2c)
(1.71 g, 7.50 mmol) was added in a single portion. The reaction
mixture was stirred for 1 h at ambient temperature and was then
concentrated in oil pump vacuum. The resulting residue was pu-
rified by column chromatography on alumina using a mixture of
hexaneediethyl ether (ratio 5:1; v/v). After drying in oil pump
vacuum the title compound was obtained as a pale yellow solid.
Please, note that 3c could not be completely separated from
P(Fc)(2-(5-Me)C4H2O)2 formed as by-product and hence was used
without additional purification in further reactions. Anal. Calcd. for
Synthesis of SiMe2(Fe(h h
5-C5H4SiMe2(CH2)3)( 5-C5H4PPh2))2 (6a)
Following the synthesis procedure described above, 3a (1.1 g,
2.45 mmol) was reacted with n-butyl lithium (0.88 mL, 2.2 mmol)
and Me2Si((CH2)3SiMe2Cl)2 (5a, 323 mg, 0.98 mmol). The resulting
residue was purified by column chromatography on alumina using
a mixture of hexaneediethyl ether (ratio 10:1 to 1:1, v/v) as eluant.
Product 6a was obtained as a viscous yellow oil. Yield: 0.7 g
(0.70 mmol, 71% based on 5a). Anal. calcd. for C56H66Fe2P2Si3
C
20H18BrFeO2P (457.08 g/mol): C, 52.55; H, 3.97. Found: C, 54.22*; H
(997.02 g/mol): 1H NMR (250.13 MHz, CDCl3,
d
): ꢀ0.07 (s, 6H, H1/
3.92*. Mp.: 77 ꢁC. IR (NaCl,
y
~/cmꢀ1): 1019 (s, CeOeC), 1410/1446/
CH3), 0.17 (s, 12H, H5/CH3), 0.52 (m, 4H, H2/CH2), 0.68 (m, 4H, H4/
CH2), 1.33 (m, 4H, H3/CH2), 3.98 (pt, 3/4JHH ¼ 1.7 Hz, 4H, Ha/C5H4Si),
1496/1593 (w, C]C), 2920/2951 (w, CeH), 3109 (w, ]CeH). 1H
3/
3/4
3/
NMR (500.30 MHz, CDCl3,
d
): 2.36 (s, 6H, CH3), 3.99 (pt,
4.07 (dpt,3JPH ¼ 1.8 Hz,
J
HH
¼ 1.8 Hz, 4H, Ha/C5H4P), 4.17 (pt,
4JHH ¼ 1.9 Hz, 2H, Hb/C5H4Br), 4.31 (pt,
J
HH
¼ 1.9 Hz, 2H, Ha/
4JHH ¼ 1.6 Hz, 4H, Hb/C5H4Si), 4.32 (pt,
J
¼ 1.8 Hz, 4H, Hb/
3/4
3/4
HH
C5H4Br), 4.38 (dpt, 4JPH ¼ 0.6 Hz, 3/4JHH ¼ 2.0 Hz, 2H, Hb/C5H4P), 4.47
C5H4P), 7.28e7.41 (m, 20H, C6H5). 13C{1H} NMR (62.90 MHz, CDCl3,
3
3/4
(dpt, JPH ¼ 1.8 Hz,
J
HH
¼ 2.0 Hz, 2H, Ha/C5H4P), 5.99 (ddq,
d
): ꢀ2.9 (s, C1/CH3), ꢀ1.9 (s, C5/CH3),18.7 (s, C3/CH2), 20.1 (s, C2/CH2),
4JPH ¼ 1.4 Hz, 3JHH ¼ 3.1 Hz, 4JHH ¼ 1.0 Hz, 2H, H4/5-MeC4H2O), 6.59
21.4 (s, C4/CH2), 71.1 (d, JCP ¼ 3 Hz, Cb/C5H4P), 72.2 (s, Cb/C5H4Si),
3

38
C. Schreiner et al. / Journal of Organometallic Chemistry 785 (2015) 32e43
2
72.4 (s, Ci/C5H4Si), 73.0 (d, JCP ¼ 15 Hz, Ca/C5H4P), 74.1 (s, Ca/
was purified by column chromatography on alumina using first a
mixture of hexaneediethyl ether (ratio 7.5:1, v/v) and then diethyl
ether as eluant. Dendritic 7a was obtained as a viscous dark orange
oil. Yield: 0.88 g (0.45 mmol, 62% based on 5b). Anal. calcd. for
C5H4Si), 75.8 (d, JCP ¼ 7 Hz, Ci/C5H4P), 128.2 (d, JCP ¼ 7 Hz, Cm/
1
3
C6H5), 128.5 (s, Cp/C6H5), 133.6 (d, JCP ¼ 19 Hz, Co/C6H5), 139.3 (d,
2
1JCP ¼ 10 Hz, Ci/C6H5). 29Si{1H} NMR (49.66 MHz, CDCl3,
d
): ꢀ2.9 (s,
Si), 1.2 (s, Sicore). 31P{1H} NMR (101.25 MHz, CDCl3,
d
): ꢀ17.9 (s).
C d):
108H120Fe4P4Si5 (1905.81 g/mol): 1H NMR (250.13 MHz, CDCl3,
0.20 (s, 24H, H4/CH3), 0.53 (m, 8H, H1/CH2), 0.70 (m, 8H, H3/CH2),
1.33 (m, 8H, H2/CH2), 4.01 (pt, 3/4JHH ¼ 1.7 Hz, 8H, Ha/C5H4Si), 4.10
Synthesis of SiMe2(Fe(h h
5-C5H4SiMe2(CH2)3)( 5-C5H4P(cC6H11)2))2
3
3/4
3/
(6b)
(dpt, JPH ¼ 1.9 Hz,
J
¼ 1.8 Hz, 8H, Ha/C5H4P), 4.20 (pt,
HH
4JHH ¼ 1.7 Hz, 8H, Hb/C5H4Si), 4.35 (pt,
J
HH
¼ 1.8 Hz, 8H, Hb/
3/4
Following the synthesis procedure described earlier, 3b (0.82 g,
1.78 mmol) was reacted with n-butyl lithium (0.64 mL, 1.60 mmol)
and Me2Si((CH2)3SiMe2Cl)2 (5a, 234 mg, 0.71 mmol). The crude
product was purified by column chromatography on alumina using
a mixture of hexaneediethyl ether (ratio 15:1 to 1:1, v/v) as eluant.
Product 6b was obtained as viscous yellow oil. Yield: 0.58 g
(0.57 mmol, 80% based on 5b). Anal. calcd. for C56H90Fe2P2Si3
C5H4P), 7.28e7.44 (m, 40H, C6H5). 13C{1H} NMR (125.81 MHz, CDCl3,
d
): ꢀ1.9 (s, C4/CH3), 17.6 (s, C1/CH2), 18.8 (s, C2/CH2), 21.9 (s, C3/CH2),
71.1 (d, 3JCP ¼ 4 Hz, Cb/C5H4P), 72.3 (s, Cb/C5H4Si), 72.4 (s, Ci/C5H4Si),
73.0 (d, JCP ¼ 15 Hz, Ca/C5H4P), 74.1 (s, Ca/C5H4Si), 75.9 (d,
2
1JCP ¼ 7 Hz, Ci/C5H4P), 128.2 (d, JCP ¼ 7 Hz, Cm/C6H5), 128.5 (s, Cp/
3
C6H5), 133.6 (d, JCP ¼ 19 Hz, Co/C6H5), 139.3 (d, JCP ¼ 10 Hz, Ci/
2
1
C6H5). 29Si{1H} NMR (49.66 MHz, CDCl3,
d
): ꢀ3.1 (s, Si), 0.7 (s, Sicore).
(1021.21 g/mol): 1H NMR (250.13 MHz, CDCl3,
d
): ꢀ0.06 (s, 6H, H1/
31P{1H} NMR (101.25 MHz, CDCl3,
d): ꢀ17.8 (s).
CH3), 0.23 (s, 12H, H5/CH3), 0.55 (m, 4H, H2/CH2), 0.73 (m, 4H, H4/
CH2), 0.95e1.35 (m, 22H, C6H11), 1.37 (m, 4H, H3/CH2), 1.59e1.98 (m,
Synthesis of Si(Fe(
h
5-C5H4SiMe2(CH2)3)(
h
5-C5H4P(cC6H11)2))4 (7b)
3/4
22H, C6H11), 4.04 (pt,
J
¼ 1.7 Hz, 4H, Ha/C5H4Si), 4.12
HH
(dpt,3JPH ¼ 1.6 Hz,
J
¼ 1.7 Hz, 4H, Ha/C5H4P), 4.23 (pt,
Compound 3b (1.60 g, 3.47 mmol) was reacted with n-butyl
lithium (1.25 mL, 3.12 mmol) and Si((CH2)3SiMe2Cl)4 (5b, 396 mg,
0.69 mmol) as described earlier. The crude product was purified by
column chromatography on alumina using first a mixture of hex-
aneediethyl ether (ratio 10:1, v/v), followed by diethyl ether as
eluant. Compound 7b was obtained as a viscous dark yellow oil.
Yield: 0.79 g (0.40 mmol, 58% based on 5b). Anal. calcd. for
3/4
3/
HH
4JHH ¼ 1.7 Hz, 4H, Hb/C5H4P), 4.28 (pt,
J
HH
¼ 1.7 Hz, 4H, Hb/
3/4
C5H4Si). 13C{1H} NMR (62.90 MHz, CDCl3,
d
): ꢀ3.0 (s, C1/CH3), ꢀ1.9
(s, C5/CH3), 18.7 (s, C3/CH2), 20.2 (s, C2/CH2), 21.5 (s, C4/CH2), 26.6 (d,
4JCP ¼ 1 Hz, C11/C6H11), 27.4 (d, JCP ¼ 9 Hz, C9/10/C6H11), 27.5 (d,
3
3JCP ¼ 11 Hz, C9/10/C6H11), 30.3 (d, 2JCP ¼ 13 Hz, C7/8/C6H11), 30.4 (d,
2JCP ¼ 11 Hz, C7/8/C6H11), 33.6 (d, JCP ¼ 12 Hz, C6/C6H11), 69.7 (d,
1
3JCP ¼ 3 Hz, Cb/C5H4P), 71.6 (d, JCP ¼ 11 Hz, Ca/C5H4P), 71.8 (s, Ci/
C d):
108H168Fe4P4Si5 (1954.19 g/mol): 1H NMR (250.13 MHz, CDCl3,
2
C5H4Si), 72.8 (s, Cb/C5H4Si), 73.9 (s, Ca/C5H4Si), 76.5 (d, 1JCP ¼ 17 Hz,
0.22 (s, 24H, H4/CH3), 0.53 (m, 8H, H1/CH2), 0.71 (m, 8H, H3/CH2),
Ci/C5H4P). 29Si{1H} NMR (49.66 MHz, CDCl3,
d
): ꢀ3.0 (s, Si), 1.0 (s,
0.95e1.30 (m, 44H, C6H11), 1.33 (m, 8H, H2/CH2), 1.59e1.98 (m, 44H,
Sicore). 31P{1H} NMR (101.25 MHz, CDCl3,
d
): ꢀ8.6 (s).
C6H11), 4.03 (pt,
J
¼
1.7 Hz, 8H, Ha/C5H4Si), 4.12
3/4
HH
3/4
3/
(dpt,3JPH ¼ 1.6 Hz,
J
¼ 1.7 Hz, 8H, Ha/C5H4P), 4.22 (pt,
HH
3/4
Synthesis of SiMe2(Fe(
h
5-C5H4SiMe2(CH2)3)( 5-C5H4P(2-(5-Me)
h
4JHH ¼ 1.7 Hz, 8H, Hb/C5H4P), 4.27 (pt,
J
¼ 1.7 Hz, 8H, Hb/
HH
C4H2O)2))2 (6c)
C5H4Si). 13C{1H} NMR (125.81 MHz, CDCl3,
d
): ꢀ1.8 (s, C4/CH3), 17.7
(s, C1/CH2), 18.9 (s, C2/CH2), 21.9 (s, C3/CH2), 26.6 (d, 4JCP ¼ 1 Hz, C10
/
/
/
3
3
Compound 3c (0.87 g, 1.90 mmol) was reacted with n-butyl
lithium (0.69 mL, 1.71 mmol) and Me2Si((CH2)3SiMe2Cl)2 (5a,
250 mg, 0.76 mmol) as described above. The crude product was
purified by column chromatography on alumina using a mixture of
hexaneediethyl ether (ratio 7.5:1 to 1:1, v/v) as eluant. The title
compound 6c was obtained as a viscous dark yellow oil. Yield:
C6H11), 27.4 (d, JCP ¼ 9 Hz, C8/9/C6H11), 27.5 (d, JCP ¼ 11 Hz, C8/9
C6H11), 30.3 (d, 2JCP ¼ 13 Hz, C6/7/C6H11), 30.4 (d, 2JCP ¼ 11 Hz, C6/7
C6H11), 33.6 (d, JCP ¼ 12 Hz, C5/C6H11), 69.7 (d, JCP ¼ 3 Hz, Cb/
1
3
C5H4P), 71.5 (d, JCP ¼ 11 Hz, Ca/C5H4P), 71.8 (s, Ci/C5H4Si), 72.8 (s,
2
Cb/C5H4Si), 73.9 (s, Ca/C5H4Si), 76.5 (d, 1JCP ¼ 17 Hz, Ci/C5H4P). 29Si
{1H} NMR (49.66 MHz, CDCl3,
d
): ꢀ3.1 (s, Si), 0.7 (s, Sicore). 31P{1H}
0.57
g
(0.56 mmol, 74% based on 5a). Anal. calcd. for
NMR (101.25 MHz, CDCl3,
d
): ꢀ8.8 (s).
C
d
52H66Fe2O4P2Si3 (1012.97 g/mol): 1H NMR (250.13 MHz, CDCl3,
): ꢀ0.06 (s, 6H, H1/CH3), 0.21 (s,12H, H5/CH3), 0.54 (m, 4H, H2/CH2),
Synthesis of Si(Fe(
h
5-C5H4SiMe2(CH2)3)( 5-C5H4P(2-(5-Me)
h
0.71 (m, 4H, H4/CH2), 1.35 (m, 4H, H3/CH2), 2.34 (s, 12H, H6/CH3),
C4H2O)2))4 (7c)
3.95 (pt, 3/4JHH ¼ 1.7 Hz, 4H, Ha/C5H4Si), 4.16 (pt, 3/4JHH ¼ 1.6 Hz, 4H,
3/4
Hb/C5H4Si), 4.27 (pt,
J
¼
1.8 Hz, 4H, Hb/C5H4P), 4.39
Compound 3c (1.55 g, 3.39 mmol) was treated with n-butyl
lithium (1.22 mL, 3.05 mmol) and Si((CH2)3SiMe2Cl)4 (5b, 387 mg,
0.68 mmol) as described earlier. The resulting residue was purified
by column chromatography on alumina using first a mixture of n-
hexaneediethyl ether (ratio 5:1, v/v) followed by diethyl ether as
eluant. The title compound 7c was obtained as a viscous dark yel-
low oil. Yield: 0.88 g (0.45 mmol, 67% based on 5b). Anal. calcd. for
HH
(dpt,3JPH ¼ 1.8 Hz,
J
¼ 1.8 Hz, 4H, Ha/C5H4P), 5.97 (ddq,
3/4
HH
4JPH ¼ 1.3 Hz, 3JHH ¼ 3.0 Hz, 4JHH ¼ 1.0 Hz, 4H, H4/5-MeC4H2O), 6.56
(ddq, 3JPH ¼ 1.9 Hz, 3JHH ¼ 3.0 Hz, 5JHH ¼ 0.2 Hz, 4H, H3/5-MeC4H2O)
13C{1H} NMR (125.81 MHz, CDCl3,
d
): ꢀ3.0 (s, C1/CH3), ꢀ1.9 (s, C5/
CH3), 14.1 (s, C6/CH3), 18.7 (s, C3/CH2), 20.1 (s, C2/CH2), 21.4 (s, C4/
CH2), 71.0 (d, JCP ¼ 5 Hz, Cb/C5H4P), 72.1 (s, Cb/C5H4Si), 72.4 (s, Ci/
3
C5H4Si), 73.4 (d, JCP ¼ 5 Hz, Ci/C5H4P), 73.6 (d, JCP ¼ 18 Hz, Ca/
C
100H120Fe4O8P4Si5 (1937.72 g/mol): 1H NMR (250.13 MHz, CDCl3,
1
2
C5H4P), 74.0 (s, Ca/C5H4Si), 107.0 (d, JCP ¼ 6 Hz, C4/5-MeC4H2O),
d
): 0.27 (s, 24H, H4/CH3), 0.53 (m, 8H, H1/CH2), 0.70 (m, 8H, H3/CH2),
3
120.8 (d, JCP ¼ 22 Hz, C3/5-MeC4H2O), 150.7 (d, 1JCP ¼ 5 Hz, C2/5-
1.32 (m, 8H, H2/CH2), 2.38 (d, 4JHH ¼ 0.5 Hz, 24H, H9/CH3), 4.01 (pt, 3/
2
MeC4H2O), 156.5 (d, JCP ¼ 3 Hz, C5/5-MeC4H2O). 29Si{1H} NMR
4JHH ¼ 1.7 Hz, 8H, Ha/C5H4Si), 4.22 (pt,
J
HH
¼ 1.7 Hz, 8H, Hb/
3
3/4
(49.66 MHz, CDCl3,
(101.25 MHz, CDCl3,
d
): ꢀ3.0 (s, Si), 1.1 (s, Sicore). 31P{1H} NMR
C5H4Si), 4.33 (dpt, 4JPH ¼ 0.3 Hz, 3/4JHH ¼ 1.9 Hz, 8H, Hb/C5H4P), 4.45
3
3/4
d
): ꢀ66.0 (s).
(dpt, JPH ¼ 1.8 Hz,
J
¼ 1.9 Hz, 8H, Ha/C5H4P), 6.02 (ddq,
HH
4JPH ¼ 1.3 Hz, 3JHH ¼ 3.1 Hz, 4JHH ¼ 1.0 Hz, 8H, H7/5-MeC4H2O), 6.61
(ddq, 3JPH ¼ 2.0 Hz, 3JHH ¼ 3.1 Hz, 5JHH ¼ 0.3 Hz, 8H, H6/5-MeC4H2O).
Synthesis of Si(Fe(h h
5-C5H4SiMe2(CH2)3)( 5-C5H4PPh2))4 (7a)
13C{1H} NMR (125.81 MHz, CDCl3,
d
): ꢀ1.9 (s, C4/CH3), 14.0 (s, C9/
Following the synthesis procedure described earlier, 3a (1.45 g,
3.23 mmol) was reacted with n-butyl lithium (1.16 mL, 2.91 mmol)
and Si((CH2)3SiMe2Cl)4 (5b, 369 mg, 0.65 mmol). The crude product
CH3), 17.6 (s, C1/CH2), 18.8 (s, C2/CH2), 21.7 (s, C3/CH2), 70.9 (d,
3JCP ¼ 5 Hz, Cb/C5H4P), 72.1 (s, Cb/C5H4Si), 72.3 (s, Ci/C5H4Si), 73.4 (d,
1JCP ¼ 5 Hz, Ci/C5H4P), 73.6 (d, JCP ¼ 18 Hz, Ca/C5H4P), 73.9 (s, Ca/
2

C. Schreiner et al. / Journal of Organometallic Chemistry 785 (2015) 32e43
39
C5H4Si), 106.9 (d, 3JCP ¼ 6 Hz, C7/5-MeC4H2O), 120.8 (d, 2JCP ¼ 22 Hz,
1JCP ¼ 80 Hz, Ci/C5H4P), 74.1 (s, Cb/C5H4Si), 74.6 (s, Ca/C5H4Si). 29Si
1
C6/5-MeC4H2O), 150.7 (d, JCP ¼ 5 Hz, C5/5-MeC4H2O), 156.4 (d,
{1H} NMR (49.66 MHz, CDCl3,
d
): ꢀ2.9 (s, Si), 1.0 (s, Sicore). 31P{1H}
3JCP ¼ 3 Hz, C8/5-MeC4H2O). 29Si{1H} NMR (49.66 MHz, CDCl3,
NMR (101.25 MHz, CDCl3, d): 57.1 (s).
d
d
): ꢀ3.1 (s, Si), 0.7 (s, Sicore). 31P{1H} NMR (101.25 MHz, CDCl3,
): ꢀ66.0 (s).
Synthesis of SiMe2(Fe(h h
5-C5H4SiMe2(CH2)3)( 5-C5H4P(2-(5-Me)
C4H2O)2(S)))2 (6c-S)
General procedure for the synthesis of carbosilane-ferrocenyl
phosphine sulfides 6a-Sec-S and 7a-Sec-S
Following the general procedure described above, 6c (355 mg,
0.35 mmol) was reacted with sulfur (22.5 mg, 0.70 mmol). After
appropriate work-up, 6c-S was obtained as a viscous pale orange
oil. Yield: 375 mg (0.35 mmol, 100% based on 6c). Anal. calcd. for
To
a toluene solution (10 mL/mmol) of 6aec and 7aec
(1.0 equiv), elemental sulfur (2.0 equiv) was added in a single
portion and the mixture was stirred for 30 min under reflux. After
cooling the reaction mixture to ambient temperature, all volatiles
were removed in oil pump vacuum and the products were obtained
as yellow to orange highly viscous oils in analytical pure form
without the need of any further purification. For more details see
below.
C
52H66Fe2O4P2S2Si3 (1077.10 g/mol): C, 57.98; H, 6.18. Found: C,
58.01; H, 6.46. IR (NaCl,
y
~/cmꢀ1): 694 (s, P]S), 798/834 (s, SieC),
1020/1036 (s, CeOeC), 1248 (m, SieMe), 1591 (m, C]C), 2874/
2913/2953 (m, CeH), 3104 (w, ]CeH). 1H NMR (500.3 MHz, CDCl3,
d
): ꢀ0.08 (s, 6H, H1/CH3), 0.18 (s, 12H, H5/CH3), 0.52 (m, 4H, H2/CH2),
0.68 (m, 4H, H4/CH2), 1.32 (m, 4H, H3/CH2), 2.36 (s, 12H, H6/CH3),
4.03 (pt, 3/4JHH ¼ 1.7 Hz, 4H, Ha/C5H4Si), 4.38 (pt, 3/4JHH ¼ 1.7 Hz, 4H,
4
3/4
Synthesis of SiMe2(Fe(
h
5-C5H4SiMe2(CH2)3)(
h
5-C5H4PPh2(S)))2 (6a-
Hb/C5H4Si), 4.40 (pt, JPH ¼ 1.8 Hz,
J
¼ 1.9 Hz, 4H, Hb/C5H4P),
HH
3
3/4
S)
4.66 (dpt, JPH ¼ 2.7 Hz,
J
HH
¼ 1.9 Hz, 4H, Ha/C5H4P), 6.06 (ddq,
4JPH ¼ 1.8 Hz, 3JHH ¼ 3.3 Hz, 4JHH ¼ 1.0 Hz, 4H, H4/5-MeC4H2O), 6.88
(ddq, 3JPH ¼ 2.6 Hz, 3JHH ¼ 3.3 Hz, 5JHH ¼ 0.5 Hz, 4H, H3/5-MeC4H2O).
Based on the general procedure described above, 6a (290 mg,
0.29 mmol) was reacted with sulfur (18.7 mg, 0.58 mmol). After
appropriate work-up, 6a-S was obtained as viscous pale orange oil.
Yield: 305 mg (0.29 mmol, 100% based on 6a). Anal. calcd. for
13C{1H} NMR (125.81 MHz, CDCl3,
d
): ꢀ3.1 (s, C1/CH3), ꢀ2.0 (s, C5/
CH3), 14.1 (s, C6/CH3), 18.6 (s, C3/CH2), 20.0 (s, C2/CH2), 21.3 (s, C4/
CH2), 72.0 (d, JCP ¼ 11 Hz, Cb/C5H4P), 72.3 (d, JCP ¼ 14 Hz, Ca/
C5H4P), 73.2 (d, 1JCP ¼ 110 Hz, Ci/C5H4P), 73.4 (s, Ci/C5H4Si), 73.5 (s,
Cb/C5H4Si), 74.6 (s, Ca/C5H4Si), 107.5 (d, 3JCP ¼ 9 Hz, C4/5-MeC4H2O),
122.8 (d, 2JCP ¼ 21 Hz, C3/5-MeC4H2O), 146.7 (d, 1JCP ¼ 127 Hz, C2/5-
3
2
C
56H66Fe2P2S2Si3 (1061.15 g/mol): C, 63.38; H, 6.27. Found: C, 63.65;
H, 6.38. IR (NaCl,
y
~/cmꢀ1): 656 (s, P]S), 813/832 (s, SieC), 1248 (m,
SieMe), 1436/1481 (m, C]C), 2870/2911/2951 (m, CeH), 3055/
3074 (m, ]CeH). 1H NMR (500.3 MHz, CDCl3,
d
): ꢀ0.09 (s, 6H, H1/
MeC4H2O), 158.5 (d, JCP ¼ 7 Hz, C5/5-MeC4H2O). 29Si{1H} NMR
3
CH3), 0.13 (s, 12H, H5/CH3), 0.50 (m, 4H, H2/CH2), 0.64 (m, 4H, H4/
CH2), 1.29 (m, 4H, H3/CH2), 4.01 (pt, 3/4JHH ¼ 1.8 Hz, 4H, Ha/C5H4Si),
(49.66 MHz, CDCl3,
(202.53 MHz, CDCl3,
d
): ꢀ2.9 (s, Si), 1.0 (s, Sicore). 31P{1H} NMR
d
): 10.2 (s).
3/4
3
3/
4.34 (pt,
J
¼ 1.8 Hz, 4H, Hb/C5H4Si), 4.42 (dpt, JPH ¼ 2.1 Hz,
HH
4JHH ¼ 1.6 Hz, 4H, Ha/C5H4P), 4.45 (pt, 3/4JHH ¼ 1.9 Hz, 3/4JHH ¼ 1.6 Hz,
Synthesis of Si(Fe(h h
5-C5H4SiMe2(CH2)3)( 5-C5H4PPh2(S)))4 (7a-S)
4H, Hb/C5H4P), 7.39e7.49 (m, 12H, Hm,p/C6H5), 7.68e7.75 (m, 8H, Ho/
C6H5). 13C{1H} NMR (125.81 MHz, CDCl3,
d
): ꢀ2.9 (s, C1/CH3), ꢀ1.9 (s,
Molecule 7a (330 mg, 0.17 mmol) was reacted with sulfur
(22.2 mg, 0.69 mmol) as described earlier. After appropriate work-
up, 7a-S was obtained as a viscous orange oil. Yield: 350 mg
(0.17 mmol, 100% based on 7a). Anal. calcd. for C108H120Fe4P4S4Si5
(2034.07 g/mol): C, 63.77; H, 5.95. Found: C, 64.37; H, 6.19. IR (NaCl,
C5/CH3), 18.7 (s, C3/CH2), 20.1 (s, C2/CH2), 21.4 (s, C4/CH2), 72.3 (d,
3JCP ¼ 10 Hz, Cb/C5H4P), 72.9 (d, 2JCP ¼ 13 Hz, Ca/C5H4P), 73.5 (s, Cb/
C5H4Si), 73.6 (s, Ci/C5H4Si), 74.7 (s, Ca/C5H4Si), 74.8 (d, 1JCP ¼ 98 Hz,
Ci/C5H4P), 128.3 (d, 3JCP ¼ 12 Hz, Cm/C6H5), 131.3 (d, 4JCP ¼ 3 Hz, Cp/
C6H5),131.8 (d, 2JCP ¼ 11 Hz, Co/C6H5),134.8 (d, 1JCP ¼ 87 Hz, Ci/C6H5).
y
~/cmꢀ1): 655 (s, P]S), 815/832(s, SieC), 1248 (m, SieMe), 1436/
29Si{1H} NMR (49.66 MHz, CDCl3,
d
): ꢀ2.9 (s, Si), 1.0 (s, Sicore). 31P
1481 (w, C]C), 2872/2914/2954 (m, CeH), 3056/3075 (m, ]CeH).
{1H} NMR (101.25 MHz, CDCl3,
d
): 41.6 (s).
1H NMR (500.3 MHz, CDCl3,
d
): 0.12 (s, 24H, H4/CH3), 0.49 (m, 8H,
3/
H1/CH2), 0.61 (m, 8H, H3/CH2), 1.23 (m, 8H, H2/CH2), 4.01 (pt,
3/4
Synthesis of SiMe2(Fe(
h
5-C5H4SiMe2(CH2)3)(
h
5-C5H4P(cC6H11)2(S)))2
4JHH ¼ 1.7 Hz, 8H, Ha/C5H4Si), 4.32 (pt,
J
HH
¼ 1.7 Hz, 8H, Hb/
(6b-S)
C5H4Si), 4.42 (dpt, 3JPH ¼ 2.1 Hz, 3/4JHH ¼ 1.7 Hz, 8H, Ha/C5H4P), 4.44
(pt, 4JPH ¼ 1.9 Hz, 3/4JHH ¼ 1.7 Hz, 8H, Hb/C5H4P), 7.88e7.49 (m, 24H,
Hm,p/C6H5), 7.68e7.74 (m, 16H, Ho/C6H5). 13C{1H} NMR (125.81 MHz,
Based on the general procedure described above, 6b (320 mg,
0.31 mmol) was treated with sulfur (20.1 mg, 0.63 mmol). After
appropriate work-up, 6b-S was obtained as a viscous dark yellow
oil. Yield: 335 mg (0.31 mmol, 100% based on 6b). Anal. calcd. for
CDCl3,
d
): ꢀ1.9 (s, C4/CH3), 17.6 (s, C1/CH2), 18.8 (s, C2/CH2), 21.7 (s,
C3/CH2), 72.3 (d, JCP ¼ 10 Hz, Cb/C5H4P), 73.0 (d, JCP ¼ 13 Hz, Ca/
C5H4P), 73.5 (s, Cb/C5H4Si), 73.6 (s, Ci/C5H4Si), 74.7 (s, Ca/C5H4Si),
74.9 (d, 1JCP ¼ 98 Hz, Ci/C5H4P),128.3 (d, 3JCP ¼ 12 Hz, Cm/C6H5),131.3
3
2
C
56H90Fe2P2S2Si3 (1085.34 g/mol): C, 61.97; H, 8.36. Found: C,
4
2
62.47; H, 8.83. IR (NaCl,
y
~/cmꢀ1): 621/641 (m, P]S), 819/831 (s,
(d, JCP ¼ 3 Hz, Cp/C6H5), 131.8 (d, JCP ¼ 11 Hz, Co/C6H5), 134.8 (d,
SieC), 1248 (m, SieMe), 2852/2929 (s, CeH), 3088(w, ]CeH). 1H
1JCP ¼ 87 Hz, Ci/C6H5). 29Si{1H} NMR (49.66 MHz, CDCl3,
d
): ꢀ3.0 (s,
NMR (500.3 MHz, CDCl3,
d
): ꢀ0.09 (s, 6H, H1/CH3), 0.21 (s, 12H, H5/
Si), 0.6 (s, Sicore). 31P{1H} NMR (101.25 MHz, CDCl3,
d): 41.5 (s).
CH3), 0.52 (m, 4H, H2/CH2), 0.70 (m, 4H, H4/CH2), 1.09e1.44 (m, 22H,
C6H11), 1.33 (m, 4H, H3/CH2), 1.63e2.05 (m, 22H, C6H11), 4.13 (pt,
Synthesis of Si(Fe(h h
5-C5H4SiMe2(CH2)3)( 5-C5H4P(cC6H11)2(S)))4
(7b-S)
3/
4JHH ¼ 1.7 Hz, 4H, Ha/C5H4Si), 4.34 (pt, 4JPH ¼ 1.8 Hz, 3/4JHH ¼ 1.7 Hz,
4H, Hb/C5H4P), 4.35 (dpt,3JPH ¼ 1.8 Hz,
J
¼ 1.7 Hz, 4H, Ha/
3/4
HH
3/4
C5H4P), 4.58 (pt,
J
¼ 1.7 Hz, 4H, Hb/C5H4Si). 13C{1H} NMR
Compound 7b (295 mg, 0.15 mmol) was reacted with sulfur
(19.4 mg, 0.60 mmol) as described above. After appropriate work-
up, 7b-S was obtained as a viscous pale orange oil. Yield: 310 mg
(0.15 mmol, 100% based on 7b). Anal. calcd. for C108H168Fe4P4S4Si5
(2082.45 g/mol): C, 62.29; H, 8.13. Found: C, 62.45; H, 8.50. IR (NaCl,
HH
(125.81 MHz, CDCl3,
d
): ꢀ3.0 (s, C1/CH3), ꢀ2.0 (s, C5/CH3), 18.6 (s, C3/
CH2), 20.1 (s, C2/CH2), 21.4 (s, C4/CH2), 25.8 (d, JCP ¼ 3 Hz, C9/10
/
/
/
3
C6H11), 25.9 (d, 3JCP ¼ 2 Hz, C9/10/C6H11), 26.7 (d, 2JCP ¼ 14 Hz, C7/8
C6H11), 26.7 (d, JCP ¼ 13 Hz, C7/8/C6H11), 26.8 (d, JCP ¼ 3 Hz, C11
2
4
C6H11), 38.0 (d, JCP ¼ 52 Hz, C6/C6H11), 70.9 (d, JCP ¼ 9 Hz, Cb/
y
~/cmꢀ1): 621/641 (m, P]S), 818/831 (s, SieC), 1247 (m, SieMe),
1
3
C5H4P), 71.6 (d, JCP ¼ 10 Hz, Ca/C5H4P), 73.1 (s, Ci/C5H4Si), 73.7 (d,
2852/2928 (s, CeH), 3088 (w, ]CeH). 1H NMR (500.3 MHz, CDCl3,
2

40
C. Schreiner et al. / Journal of Organometallic Chemistry 785 (2015) 32e43
d
): 0.19 (s, 24H, H4/CH3), 0.47 (m, 8H, H1/CH2), 0.66 (m, 8H, H3/CH2),
and an excess of methanol (1.0 mL). Appropriate work-up, resulted
0.95e1.30 (m, 44H, C6H11), 1.30 (m, 8H, H2/CH2), 1.59e1.98 (m, 44H,
in the formation of phosphine 4a, which was then treated with
3/4
C6H11), 4.11 (pt,
J
¼
1.7 Hz, 8H, Ha/C5H4Si), 4.33 (pt,
[RuCl2(h
6-p-cymene)]2 (8) (395 mg, 0.64 mmol) to afford complex
HH
4JPH ¼ 1.8 Hz, 3/4JHH ¼ 1.7 Hz, 8H, Hb/C5H4P), 4.34 (dpt,3JPH ¼ 1.8 Hz,
9a as a dark orange solid. Yield: 830 mg (1.23 mmol, 95% based on
3a). Anal. calcd. for C32H33Cl2FePRu (676.40 g/mol): C, 56.82; H,
3/4
3/4
J
¼ 1.7 Hz, 8H, Ha/C5H4P), 4.55 (pt,
J
HH
¼ 1.7 Hz, 8H, Hb/
HH
C5H4Si). 13C{1H} NMR (125.81 MHz, CDCl3,
d
): ꢀ2.0 (s, C4/CH3), 17.5
4.92. Found: C, 56.71; H, 5.15. Mp.: 205 ꢁC (dec.). IR (NaCl, ~/cmꢀ1):
y
(s, C1/CH2), 18.7 (s, C2/CH2), 21.7 (s, C3/CH2), 25.8 (d, 3JCP ¼ 2 Hz, C8/9
/
/
/
1434/1482 (m, C]C), 2869/2924/2961 (m, CeH), 3050 (m, ]CeH).
C6H11), 25.9 (d, JCP ¼ 1 Hz, C8/9/C6H11), 26.7 (d, JCP ¼ 13 Hz, C6/7
1H NMR (500.3 MHz, CDCl3,
d
): 0.97 (d, 3JHH ¼ 6.9 Hz, 6H, CH(CH3)2),
3
2
C6H11), 26.7 (d, JCP ¼ 13 Hz, C6/7/C6H11), 26.8 (d, JCP ¼ 3 Hz, C10
1.80 (s, 3H, CH3), 2.58 (sept, 3JHH ¼ 6.9 Hz,1H, CH(CH3)2), 3.77 (s, 5H,
2
4
C6H11), 38.0 (d, JCP ¼ 53 Hz, C5/C6H11), 70.9 (d, JCP ¼ 9 Hz, Cb/
C5H5), 4.36 (dpt, JPH ¼ 1.4 Hz,
J
¼ 1.8 Hz, 2H, Hb/C5H4), 4.49
1
3
4
3/4
HH
C5H4P), 71.6 (d, JCP ¼ 10 Hz, Ca/C5H4P), 73.0 (s, Ci/C5H4Si), 73.9 (d,
(dpt, 3JPH ¼ 2.0 Hz, 3/4JHH ¼ 1.8 Hz, 2H, Ha/C5H4), 5.11 (m, 2H, C6H4),
2
1JCP ¼ 79 Hz, Ci/C5H4P), 73.9 (s, Cb/C5H4Si), 74.5 (s, Ca/C5H4Si). 29Si
5.14 (m, JPH ¼ 1.5 Hz, 2H, C6H4), 7.35e7.47 (m, 6H, Hm,p/C6H5),
3
{1H} NMR (99.39 MHz, CDCl3,
d
): ꢀ3.1 (s, Si), 0.7 (s, Sicore). 31P{1H}
7.87e7.93 (m, 4H, Ho/C6H5). 13C{1H} NMR (125.81 MHz, CDCl3,
d):
NMR (101.25 MHz, CDCl3,
d
): 57.1 (s).
17.0 (s, CH3), 21.6 (s, CH(CH3)2), 29.8 (s, CH(CH3)2), 69.8 (s, C5H5),
69.9 (d, 3JCP ¼ 8 Hz, Cb/C5H4), 74.6 (d, 2JCP ¼ 11 Hz, Ca/C5H4), 76.7 (d,
1JCP ¼ 49 Hz, Ci/C5H4), 85.7 (d, 2JCP ¼ 6 Hz, C6H4), 90.0 (d, 2JCP ¼ 4 Hz,
C6H4), 94.7 (s, Ci/C6H4), 108.8 (s, Ci/C6H4), 127.2 (d,3JCP ¼ 10 Hz, Cm/
C6H5), 129.9 (d, 4JCP ¼ 2 Hz, Cp/C6H5), 133.8 (d, 2JCP ¼ 9 Hz, Co/C6H5),
Synthesis of Si(Fe(
C4H2O)2(S)))4 (7c-S)
h
5-C5H4SiMe2(CH2)3)( 5-C5H4P(2-(5-Me)
h
Based on the general procedure described earlier, 7c (310 mg,
0.16 mmol) was reacted with sulfur (20.5 mg, 0.64 mmol). After
appropriate work-up, 7c-S was obtained as a viscous pale orange oil.
Yield: 330 mg (0.16 mmol, 100% based on 7c). Anal. calcd. for
136.0 (d, 1JCP ¼ 47 Hz, Ci/C6H5). 31P{1H} NMR (101.25 MHz, CDCl3,
d):
18.4 (s).
Synthesis of [RuCl2(h
6-p-cymene)(P(cC6H11)2Fc)] (9b)
C
100H120Fe4O8P4S4Si5 (2065.98 g/mol): C, 58.14; H, 5.85. Found: C,
58.14; H, 6.04. IR (NaCl,
~/cmꢀ1): 693 (s, P]S), 794/834 (s, SieC),
1020/1036 (s, CeOeC),1248 (m, SieMe),1590 (m, C]C), 2874/2915/
y
Compound 3b (605 mg, 1.31 mmol) was reacted with n-butyl
lithium (0.58 mL, 1.44 mmol) and methanol (1.0 mL). After appro-
2954 (m, CeH), 3104 (w, ]CeH).1H NMR (500.3 MHz, CDCl3,
d
): 0.18
priate work-up, phosphine 4b was then reacted with [RuCl2(h
6-p-
(s, 24H, H4/CH3), 0.48 (m, 8H, H1/CH2), 0.66 (m, 8H, H3/CH2),1.26 (m,
cymene)]2 (8) (400 mg, 0.65 mmol) to afford complex 9b as a pale
red solid. Yield: 885 mg (1.28 mmol, 98% based on 3b). Anal. calcd.
for C32H45Cl2FePRu (688.49 g/mol): C, 55.82; H, 6.59. Found: C,
8H, H2/CH2), 2.35 (s, 24H, H9/CH3), 4.03 (pt, 3/4JHH ¼ 1.8 Hz, 8H, Ha/
3/4
C5H4Si), 4.36 (pt,
J
¼ 1.8 Hz, 8H, Hb/C5H4Si), 4.40 (dpt,
HH
4JPH ¼ 1.9 Hz, 3/4JHH ¼ 1.8 Hz, 8H, Hb/C5H4P), 4.66 (dpt, 3JPH ¼ 2.6 Hz, 3/
4JHH ¼ 1.8 Hz, 8H, Ha/C5H4P), 6.05 (ddq, 4JPH ¼ 1.7 Hz, 3JHH ¼ 3.3 Hz,
55.93; H, 6.76. Mp.: 195 ꢁC (dec.). IR (NaCl, ~/cmꢀ1): 1445 (m, C]C),
y
2849/2921 (s, CeH), 3046 (w, ]CeH). 1H NMR (500.3 MHz, CDCl3,
4JHH ¼ 1.0 Hz, 8H, H4/5-MeC4H2O), 6.87 (ddq, JPH ¼ 2.5 Hz,
d
): 1.14 (d, JHH ¼ 6.9 Hz, 6H, CH(CH3)2), 1.19e1.42 (m, C6H11),
3
3
3JHH ¼ 3.3 Hz, JHH ¼ 0.4 Hz, 8H, H3/5-MeC4H2O). 13C{1H} NMR
1.68e2.07 (m, C6H11), 1.89 (s, 3H, CH3), 2.35e2.64 (m, C6H11), 2.68
(sept,3JHH ¼ 6.9 Hz, 1H, CH(CH3)2), 4.27 (s, 5H, C5H5), 4.49 (dpt,
4JPH ¼ 0.9 Hz, 3/4JHH ¼ 1.8 Hz, 2H, Hb/C5H4), 4.53 (dpt, 3JPH ¼ 1.7 Hz, 3/
4JHH ¼ 1.8 Hz, 2H, Ha/C5H4), 4.84 (m, 2H, C6H4), 4.98 (m, 2H, C6H4).
5
(125.81 MHz, CDCl3,
d
): ꢀ2.0 (s, C4/CH3), 14.1 (s, C9/CH3), 17.5 (s, C1/
CH2),18.7 (s, C2/CH2), 21.6 (s, C3/CH2), 72.0 (d, 3JCP ¼ 11 Hz, Cb/C5H4P),
72.3 (d, 2JCP ¼ 15 Hz, Ca/C5H4P), 73.2 (d, 1JCP ¼ 110 Hz, Ci/C5H4P), 73.4
(s, Ci/C5H4Si), 73.5 (s, Cb/C5H4Si), 74.5 (s, Ca/C5H4Si), 107.5 (d,
3JCP ¼ 9 Hz, C4/5-MeC4H2O), 122.8 (d, 2JCP ¼ 21 Hz, C3/5-MeC4H2O),
146.6 (d, 1JCP ¼ 127 Hz, C2/5-MeC4H2O), 158.5 (d, 3JCP ¼ 7 Hz, C5/5-
13C{1H} NMR (125.81 MHz, CDCl3,
d): 17.7 (s, CH3), 22.5 (s,
CH(CH3)2), 26.3 (d, 4JCP ¼ 1 Hz, C6/C6H11), 27.8 (d, 3JCP ¼ 11 Hz, C4,5
/
C6H11), 28.1 (d, 3JCP ¼ 11 Hz, C4,5/C6H11), 29.4 (s, C2,3/C6H11), 30.0 (s,
C2,3/C6H11), 30.4 (s, CH(CH3)2), 39.6 (d, 1JPC ¼ 21 Hz, C1/C6H11), 69.5
(d, 3JCP ¼ 7 Hz, Cb/C5H4), 70.0 (s, C5H5), 72.5 (d, 2JCP ¼ 8 Hz, Ca/C5H4),
MeC4H2O). 29Si{1H} NMR (49.66 MHz, CDCl3,
d
): ꢀ3.0 (s, Si), 0.6 (s,
Sicore). 31P{1H} NMR (101.25 MHz, CDCl3,
d): 10.1 (s).
82.0 (d, 1JCP ¼ 30 Hz, Ci/C5H4), 85.4 (d, JCP ¼ 5 Hz, C6H4), 89.8 (d,
2
General procedure for the synthesis of [RuCl2(
h
6-p-cymene)(PR2Fc)]
2JCP ¼ 4 Hz, C6H4), 93.8 (s, Ci/C6H4), 107.0 (s, Ci/C6H4). 31P{1H} NMR
(9aec)
(101.25 MHz, CDCl3, d): 16.6 (s).
To a solution of 3aec (1.0 equiv) in tetrahydrofuran (10 mL/
mmol) a 2.5 M solution of n-butyl lithium in hexane (1.1 equiv) was
added dropwise at ꢀ40 ꢁC. After stirring the reaction mixture for
45 min at this temperature, methanol (1.0 mL) was added dropwise.
The reaction mixture was warmed to ambient temperature and all
volatile materials were removed in oil pump vacuum. The residue
was then dissolved in diethyl ether (30 mL) and filtered through a
pad of Celite. After removal of the solvent, phosphines 4aec were
Synthesis of [RuCl2(h
6-p-cymene)(P(2-(5-Me)C4H2O)2Fc)] (9c)
Molecule 3c (625 mg, 1.37 mmol) was treated with n-butyl
lithium (0.60 mL, 1.50 mmol) and methanol (1.0 mL). After appro-
priate work-up, phosphine 4c was reacted with [RuCl2(h
6-p-cym-
ene)]2 (8) (419 mg, 0.68 mmol) to afford 9c as a red solid. Yield:
900 mg (1.31 mmol, 96% based on 3c). Anal. calcd. for
C
30H33Cl2FeO2PRu (684.38 g/mol): C, 52.65; H, 4.86. Found: C,
52.64; H, 4.71. Mp.: 175 ꢁC (dec.). IR (NaCl, ~/cmꢀ1): 1024 (s,
CeOeC), 1592 (m, C]C), 2855/2917/2958 (m, CeH), 3045 (w, ]
dissolved in dichloromethane (10 mL/mmol), [RuCl2(
h
6-p-cym-
y
ene)]2 (8) (0.5 equiv) was added in a single portion and the reaction
mixture was stirred for 2 h at ambient temperature. Afterward, all
volatiles were removed in vacuum and the residue was washed
thrice with 10 mL portions of pentane. After drying in oil pump
vacuum, the appropriate complexes were obtained as orange to red
solids. For more details see below.
3
CeH). 1H NMR (500.3 MHz, CDCl3,
d
): 1.06 (d, JHH ¼ 6.9 Hz, 6H,
CH(CH3)2), 1.86 (s, 3H, CH3), 2.44 (s, 6H, 5-CH3C4H2O), 2.73
(sept,3JHH ¼ 6.9 Hz, 1H, CH(CH3)2), 4.06 (s, 5H, C5H5), 4.35 (dpt,
4JPH ¼ 1.8 Hz, 3/4JHH ¼ 1.7 Hz, 2H, Hb/C5H4), 4.54 (dpt, 3JPH ¼ 1.6 Hz, 3/
4JHH
¼
1.7 Hz, 2H, Ha/C5H4), 5.26 (m, 2H, C6H4), 5.40 (m,
3JPH ¼ 1.4 Hz, 2H, C6H4), 6.11 (ddq, JPH ¼ 1.1 Hz, JHH ¼ 3.4 Hz,
4
3
3
Synthesis of [RuCl2(
h
6-p-cymene)(PPh2Fc)] (9a)
4JHH ¼ 1.1 Hz, 8H, H4/5-MeC4H2O), 6.87 (ddq, JPH ¼ 1.4 Hz,
3JHH ¼ 3.4 Hz, JHH ¼ 0.4 Hz, 8H, H3/5-MeC4H2O). 13C{1H} NMR
5
Following the synthesis procedure described above, 3a (580 mg,
1.29 mmol) was reacted with n-butyl lithium (0.57 mL, 1.42 mmol)
(125.81 MHz, CDCl3, d): 14.1 (s, 5-CH3C4H2O), 17.4 (s, CH3), 21.8 (s,
CH(CH3)2), 30.2 (s, CH(CH3)2), 70.1 (s, C5H5), 70.2 (d, 3JCP ¼ 9 Hz, Cb/

C. Schreiner et al. / Journal of Organometallic Chemistry 785 (2015) 32e43
41
C5H4), 73.4 (d, 2JCP ¼ 12 Hz, Ca/C5H4), 74.3 (d, 1JCP ¼ 56 Hz, Ci/C5H4),
NMR (62.90 MHz, CDCl3,
d
): ꢀ3.2 (s, C1/CH3), ꢀ2.1 (s, C5/CH3), 17.6
85.6 (d, JCP ¼ 6 Hz, C6H4), 90.9 (d, JCP ¼ 5 Hz, C6H4), 94.6 (s, Ci/
(s, CH3), 18.4 (s, C3/CH2), 19.9 (s, C2/CH2), 21.2 (s, C4/CH2), 22.4 (s,
CH(CH3)2), 26.2 (s, C6/C6H11), 27.8 (d, 3JCP ¼ 12 Hz, C4,5/C6H11), 28.1
(d, 3JCP ¼ 12 Hz, C4,5/C6H11), 29.4 (s, C2,3/C6H11), 30.0 (s, C2,3/C6H11),
2
2
C6H4), 107.5 (d, 3JCP ¼ 6 Hz, C4/5-MeC4H2O), 108.8 (s, Ci/C6H4), 124.0
2
1
(d, JCP ¼ 14 Hz, C3/5-MeC4H2O), 145.1 (d, JCP ¼ 74 Hz, C2/5-
MeC4H2O), 156.5 (d, JCP ¼ 5 Hz, C5/5-MeC4H2O). 31P{1H} NMR
30.3 (s, CH(CH3)2), 39.9 (d, JCP ¼ 20 Hz, C1/C6H11), 69.9 (d,
3
1
2
(101.25 MHz, CDCl3,
d): ꢀ3.8 (s).
3JCP ¼ 7 Hz, Cb/C5H4P), 72.1 (d, JCP ¼ 9 Hz, Ca/C5H4P), 72.9 (s, Ci/
C5H4Si), 73.5 (s, Cb/C5H4Si), 74.2 (s, Ca/C5H4Si), 82.1 (d, 1JCP ¼ 30 Hz,
Ci/C5H4P), 85.2 (d, 2JCP ¼ 5 Hz, C6H4), 89.6 (d, 2JCP ¼ 4 Hz, C6H4), 93.9
(s, Ci/C6H4), 106.8 (s, Ci/C6H4). 29Si{1H} NMR (49.66 MHz, CDCl3,
General procedure for the synthesis of carbosilane-ferrocenyl
phosphine RuCl2(
6-p-cymene) complexes 10aec and 11aec
h
d
): ꢀ2.8 (s, Si), 1.0 (s, Sicore). 31P{1H} NMR (101.25 MHz, CDCl3,
d):
To a dichloromethane solution (10, 25 mL/mmol; 11, 50 mL/
mmol) containing 3aec (1.0 equiv), [RuCl2(
6-p-cymene)]2 (8) (10,
16.5 (s).
h
1.0 equiv; 11, 2.0 equiv) was added in a single portion. This reaction
solution was stirred for 2 h (10) or 5 h (11) at ambient temperature.
Afterward, all volatiles were removed in vacuum and the crude
product was washed thrice with 10 mL portions of a mixture of
pentaneediethyl ether (10, ratio 1:1, v/v) or diethyl ether (11). After
drying in oil pump vacuum, the products were obtained as red
solids. For more details see below.
Synthesis of SiMe2(Fe(h h
5-C5H4SiMe2(CH2)3)( 5-C5H4P(2-(5-Me)
C4H2O)2)RuCl2(h
6-p-cymene))2 (10c)
Molecule 3c (205 mg, 0.20 mmol) was reacted with 8 (124 mg,
0.20 mmol) as described earlier. After appropriate work-up, com-
plex 10c was obtained as a red solid. Yield: 315 mg (0.19 mmol, 96%
based on 3c). Anal. calcd. for C72H94Cl4Fe2O4P2Ru2Si3 (1625.36 g/
mol): C, 53.20; H, 5.83. Found: C, 53.25; H, 5.96. Mp.: 95 ꢁC. IR (NaCl,
Synthesis of SiMe2(Fe(
h
5-C5H4SiMe2(CH2)3)(
h
5-C5H4PPh2)RuCl2(h6
-
y
~/cmꢀ1): 800/830 (s, SieC), 1024/1040 (s, CeOeC), 1246 (m, SieMe),
p-cymene))2 (10a)
1592 (m, C]C), 2871/2917/2955 (m, CeH), 3040 (w, ]CeH). 1H
NMR (500.3 MHz, CDCl3,
d
): ꢀ0.10 (s, 6H, H1/CH3), 0.14 (s, 12H, H5/
Following the synthesis procedure described above, 3a (340 mg,
0.34 mmol) was reacted with 8 (209 mg, 0.34 mmol) to give, after
appropriate work-up, complex 10a as a red solid. Yield: 535 mg
(0.33 mmol, 98% based on 3a). Anal. calcd. for C76H94Cl4Fe2P2Ru2Si3
(1609.41 g/mol): C, 56.72; H, 5.89. Found: C, 57.17; H, 6.11. Mp.:
CH3), 0.49 (m, 4H, H2/CH2), 0.64 (m, 4H, H4/CH2), 1.06 (d,
3JHH ¼ 7.0 Hz, 12H, CH(CH3)2), 1.29 (m, 4H, H3/CH2), 1.85 (s, 6H, CH3),
2.45 (s, 12H, 5-CH3C4H2O), 2.73 (sept, 3JHH ¼ 6.9 Hz, 2H, CH(CH3)2),
3.92 (pt, 3/4JHH ¼ 1.7 Hz, 4H, Ha/C5H4Si), 4.24 (pt, 3/4JHH ¼ 1.7 Hz, 4H,
4
3/4
Hb/C5H4Si), 4.30 (dpt, JPH ¼ 1.9 Hz,
J
HH
¼ 1.7 Hz, 4H, Hb/C5H4P),
120 ꢁC. IR (NaCl,
y
~/cmꢀ1): 802/831 (m, SieC),1248 (m, SieMe),1434/
4.53 (dpt, 3JPH ¼ 1.9 Hz, 3/4JHH ¼ 1.7 Hz, 4H, Ha/C5H4P), 5.25 (m, 4H,
1482 (m, C]C), 2871/2911/2958 (m, CeH), 3053 (m, ]CeH). 1H
C6H4), 5.39 (m, JPH ¼ 1.5 Hz, 4H, C6H4), 6.14 (ddq, JPH ¼ 1.3 Hz,
3
4
4
NMR (500.3 MHz, CDCl3,
d
): ꢀ0.13 (s, 6H, H1/CH3), 0.08 (s, 12H, H5/
3JHH ¼ 3.3 Hz, JHH ¼ 1.0 Hz, 4H, H4/5-CH3C4H2O), 6.94 (ddq,
CH3), 0.44 (m, 4H, H2/CH2), 0.57 (m, 4H, H4/CH2), 0.96 (d,
3JHH ¼ 7.0 Hz, 12H, CH(CH3)2), 1.22 (m, 4H, H3/CH2), 1.79 (s, 6H, CH3),
3JPH ¼ 1.5 Hz, 3JHH ¼ 3.3 Hz, 5JHH ¼ 0.4 Hz, 4, H, H3/5-CH3C4H2O). 13
C
{1H} NMR (62.90 MHz, CDCl3,
d
): ꢀ3.1 (s, C1/CH3), ꢀ2.1 (s, C5/CH3),
2.56 (sept, 3JHH ¼ 7.0 Hz, 2H, CH(CH3)2), 3.60 (pt, 3/4JHH ¼ 1.7 Hz, 4H,
14.2 (s, 5-CH3C4H2O), 17.4 (s, CH3), 18.5 (s, C3/CH2), 20.0 (s, C2/CH2),
21.3 (s, C4/CH2), 21.9 (s, CH(CH3)2), 30.2 (s, CH(CH3)2), 70.8 (d,
3JCP ¼ 9 Hz, Cb/C5H4P), 72.5 (s, Ci/C5H4Si), 73.0 (d, 2JCP ¼ 12 Hz, Ca/
Ha/C5H4Si), 3.85 (pt,
J
HH
¼ 1.7 Hz, 4H, Hb/C5H4Si), 4.31 (dpt,
3/4
4JPH ¼ 1.3 Hz, 3/4JHH ¼ 1.7 Hz, 4H, Hb/C5H4P), 4.48 (dpt, 3JPH ¼ 1.9 Hz,
3/4
1
J
¼ 1.7 Hz, 4H, Ha/C5H4), 5.10 (m, 4H, C6H4), 5.14 (m,
C5H4P), 74.1 (s, C5H4Si), 74.1 (s, C5H4Si), 74.9 (d, JCP ¼ 55 Hz, Ci/
HH
3JPH ¼ 1.2 Hz, 4H, C6H4), 7.29e7.46 (m, 12H, Hm,p/C6H5), 7.85e7.92
C5H4P), 85.6 (d, 2JCP ¼ 7 Hz, C6H4), 90.9 (d, 2JCP ¼ 5 Hz, C6H4), 94.6 (s,
(m, 8H, Ho/C6H5). 13C{1H} NMR (62.90 MHz, CDCl3,
d
): ꢀ3.4 (s, C1/
Ci/C6H4), 107.8 (d, JCP ¼ 7 Hz, C4/5-CH3C4H2O), 108.9 (s, Ci/C6H4),
3
CH3), ꢀ2.4 (s, C5/CH3), 16.9 (s, CH3), 18.1 (s, C3/CH2), 19.5 (s, C2/CH2),
20.8 (s, C4/CH2), 21.5 (s, CH(CH3)2), 29.6 (s, CH(CH3)2), 71.1 (d,
3JCP ¼ 8 Hz, Cb/C5H4P), 71.8 (s, Ci/C5H4Si), 73.6 (s, Ca/C5H4Si), 74.3 (s,
Cb/C5H4Si), 74.5 (d, 2JCP ¼ 11 Hz, Ca/C5H4P), 76.5 (d, 1JCP ¼ 49 Hz, Ci/
C5H4P), 85.6 (d, 2JCP ¼ 6 Hz, C6H4), 90.0 (d, 2JCP ¼ 4 Hz, C6H4), 94.7 (s,
Ci/C6H4), 108.6 (s, Ci/C6H4), 128.2 (d,3JCP ¼ 10 Hz, Cm/C6H5), 129.7 (s,
Cp/C6H5), 133.6 (d, 2JCP ¼ 10 Hz, Co/C6H5), 136.1 (d, 1JCP ¼ 47 Hz, Ci/
124.3(d, 2JCP ¼ 14 Hz, C3/5-CH3C4H2O), 144.9 (d, 1JCP ¼ 74 Hz, C2/5-
3
CH3C4H2O), 156.5 (d, JCP ¼ 5 Hz, C5/5-CH3C4H2O). 29Si{1H} NMR
(49.66 MHz, CDCl3,
(101.25 MHz, CDCl3,
d
): ꢀ3.2 (s, Si), 0.9 (s, Sicore). 31P{1H} NMR
d
): ꢀ3.7 (s).
Synthesis of Si(Fe(h h h
5-C5H4SiMe2(CH2)3)( 5-C5H4PPh2)RuCl2( 6-p-
cymene))4 (11a)
C6H5). 29Si{1H} NMR (49.66 MHz, CDCl3,
d
): ꢀ3.1 (s, Si), 0.8 (s, Sicore).
31P{1H} NMR (101.25 MHz, CDCl3,
d
): 18.4 (s).
Following the synthesis procedure described above, 3a (435 mg,
0.23 mmol) was reacted with 8 (280 mg, 0.46 mmol) to give
complex 11a as a red solid. Yield: 695 mg (0.22 mmol, 97% based on
3a). Anal. calcd. for C148H176Cl8Fe4P4Ru4Si5 (3130.59 g/mol): C,
Synthesis of SiMe2(Fe(
h
5-C5H4SiMe2(CH2)3)( 5-C5H4P(cC6H11)2)
h
RuCl2(
h
6-p-cymene))2 (10b)
56.78; H, 5.67. Found: C, 57.29; H, 5.79. Mp.: 165 ꢁC. IR (NaCl,
y~/
Following the synthesis procedure described earlier, 3b
(225 mg, 0.22 mmol) was reacted with 8 (135 mg, 0.22 mmol) to
give 10b as a red solid. Yield: 340 mg (0.21 mmol, 95% based on 3b).
Anal. calcd. for C76H118Cl4Fe2P2Ru2Si3 (1633.60 g/mol): C, 55.88; H,
cmꢀ1): 813/831 (m, SieC), 1246 (m, SieMe), 1434/1482 (m, C]C),
2870/2914/2958 (m, CeH), 3052 (m, ]CeH). 1H NMR (500.3 MHz,
CDCl3, d
): 0.05 (s, 24H, H4/CH3), 0.35 (m, 8H, H1/CH2), 0.51 (m, 8H,
H3/CH2), 0.96 (d, 3JHH ¼ 7.0 Hz, 12H, CH(CH3)2), 1.12 (m, 8H, H2/CH2),
7.28. Found: C, 56.43; H, 7.77. Mp.: 141 ꢁC. IR (NaCl,
y
~/cmꢀ1): 801/
1.79 (s,12H, CH3), 2.55 (sept, 3JHH ¼ 7.0 Hz, 4H, CH(CH3)2), 3.58 (pt, 3/
830 (s, SieC), 1248 (m, SieMe), 2851/2919 (s, CeH). 1H NMR
4JHH ¼ 1.7 Hz, 8H, Ha/C5H4Si), 3.83 (pt,
J
HH
¼ 1.7 Hz, 8H, Hb/
3/4
(500.3 MHz, CDCl3,
d
): ꢀ0.8 (s, 6H, H1/CH3), 0.23 (s, 12H, H5/CH3),
C5H4Si), 4.30 (pt, 4JPH ¼ 1.5 Hz, 3/4JHH ¼ 1.7 Hz, 8H, Hb/C5H4P), 4.47
(dpt, 3JPH ¼ 1.8 Hz, 3/4JHH ¼ 1.7 Hz, 8H, Ha/C5H4P), 5.09 (m, 8H, C6H4),
0.52 (m, 4H, H2/CH2), 0.71 (m, 4H, H4/CH2), 0.99e1.46 (m, H, C6H11),
3
3
1.11 (d, JHH ¼ 7.0 Hz, 12H, CH(CH3)2), 1.36 (m, 4H, H3/CH2),
5.13 (m, JPH ¼ 1.2 Hz, 8H, C6H4), 7.37e7.45 (m, 24H, Hm,p/C6H5),
1.53e2.10 (m, C6H11), 1.86 (s, 6H, CH3), 2.22e2.59 (m, C6H11), 2.62
7.85e7.91 (m, 16H, Ho/C6H5). 13C{1H} NMR (62.90 MHz, CDCl3,
(sept, 3JHH ¼ 7.0 Hz, 2H, CH(CH3)2), 4.09 (pt, 3/4JHH ¼ 1.7 Hz, 4H, Ha/
d
): ꢀ2.0 (s, C4/CH3), 17.3 (s, CH3), 17.5 (s, C1/CH2), 18.7 (s, C2/CH2),
3/4
C5H4Si), 4.42 (pt,
J
HH
¼ 1.7 Hz, 4H, Hb/C5H4Si), 4.45 (m, 8H,
21.7 (s, C3/CH2), 21.9 (s, CH(CH3)2), 30.1 (s, CH(CH3)2), 70.7 (d,
C5H4P), 4.83 (m, 4H, C6H4), 4.94 (m, 3JPH ¼ 1.2 Hz, 4H, C6H4). 13C{1H}
3JCP ¼ 8 Hz, Cb/C5H4P), 72.4 (s, Ci/C5H4Si), 74.1 (s, Ca/C5H4Si), 74.9 (s,

42
C. Schreiner et al. / Journal of Organometallic Chemistry 785 (2015) 32e43
Cb/C5H4Si), 75.0 (d, 2JCP ¼ 10 Hz, Ca/C5H4P), 76.9 (d, 1JCP ¼ 50 Hz, Ci/
C5H4P), 86.0 (d, 2JCP ¼ 6 Hz, C6H4), 90.3 (d, 2JCP ¼ 4 Hz, C6H4), 95.2 (s,
Ci/C6H4), 109.5 (s, Ci/C6H4), 127.6 (d, 3JCP ¼ 10 Hz, Cm/C6H5), 130.2 (s,
General procedure for the catalytic reactions
Benzoic acid (366 mg, 3.0 mmol, 1.0 equiv), acenaphthene
(116 mg, 750 mmol, 0.25 equiv, internal standard) and the respective
2
4JCP ¼ 2 Hz, Cp/C6H5), 134.2 (d, JCP ¼ 9 Hz, Co/C6H5), 136.6 (d,
1JCP ¼ 47 Hz, Ci/C6H5). 29Si{1H} NMR (49.66 MHz, CDCl3,
d
): ꢀ3.1 (s,
catalyst (9, 10 or 11, 1.0 mol-% based on Ru) were dissolved in
chlorobenzene (15 mL). After addition of propargyl alcohol
(252 mg, 4.5 mmol, 1.5 equiv) the reaction mixture was stirred at
80 ꢁC and samples (0.5 mL) were taken in different intervals
(30e90 min). The samples were dried in vacuum and the conver-
sions were determined by 1H NMR spectroscopy.
Si), 0.5 (s, Sicore). 31P{1H} NMR (101.25 MHz, CDCl3,
d): 18.1 (s).
Synthesis of Si(Fe(
RuCl2(
6-p-cymene))4 (11b)
h h
5-C5H4SiMe2(CH2)3)( 5-C5H4P(cC6H11)2)
h
Compound 3b (390 mg, 0.20 mmol) was reacted with 8 (245 mg,
0.40 mmol) as described earlier, whereby 11b was obtained as red
solid. Yield: 610 mg (0.19 mmol, 96% based on 3b). Anal. calcd. for
Crystal data for 9c
Single crystals of 9c were obtained from a saturated chloroform
solution containing 9c at 298 K. Data were collected with an Oxford
Gemini S diffractometer, with graphite monochromatized Cu Ka
C
148H224Cl8Fe4P4Ru4Si5 (3178.97 g/mol): C, 55.92; H, 7.10. Found: C,
56.06; H, 7.30. Mp.: 148 ꢁC. IR (NaCl, ~/cmꢀ1): 802/830 (s, SieC),
y
1248 (m, SieMe), 2851/2919 (s, CeH), 3044 (w, ]CeH). 1H NMR
(500.3 MHz, CDCl3,
): 0.26 (s, 24H, H4/CH3), 0.51 (m, 8H, H1/CH2),
radiation (
l
¼ 1.54184 Å). The structure was solved by direct
d
0.71 (m, 8H, H3/CH2), 1.15 (d, JHH ¼ 7.0 Hz, 24H, CH(CH3)2),
1.20e1.41 (m, 40H, H2/CH2 þ H4,5/C6H11 þ H6/C6H11), 1.74e2.01 (m,
52H, CH3 þ H2,3/C6H11 þ H4,5/C6H11 þ H6/C6H11), 2.41e2.58 (m, 16H,
H1/C6H11 þ H2,3/C6H11), 2.65 (sept, 3JHH ¼ 7.0 Hz, 4H, CH(CH3)2), 4.11
(pt, 3/4JHH ¼ 1.7 Hz, 8H, Ha/C5H4Si), 4.44 (pt, 3/4JHH ¼ 1.7 Hz, 8H, Hb/
C5H4Si), 4.47 (m, 16H, C5H4P), 4.82 (m, 8H, C6H4), 4.96 (m, 8H, C6H4).
3
methods using SHELXS-97 [26] and refined by full-matrix least
square procedures on F2 using SHELXL-97 [27]. C67H80Cl10Fe2O4
-
P2Ru2, Mr ¼ 1679.59 g molꢀ1, triclinic, P1;
l
¼ 1.54184 Å,
a ¼ 11.6574(5) Å, b ¼ 12.6942(5) Å, c ¼ 13.7460(5) Å,
a
¼ 78.846(3)ꢁ,
b
¼ 85.974(4)ꢁ,
g
¼ 67.643(4)ꢁ, V ¼ 1845.70(14) Å3, Z ¼ 1,
rcalcd
¼
1.511 mg mꢀ3
,
m
¼
10.427 mmꢀ1
,
T
¼
100 K, Q
range ¼ 4.10e62.00ꢁ, reflections collected: 12,705, independent:
13C{1H} NMR (125.81 MHz, CDCl3,
d
): ꢀ2.2 (s, C4/CH3), 17.3 (s, C1/
CH2), 17.6 (s, CH3), 18.5 (s, C2/CH2), 21.5 (s, C3/CH2), 22.3 (s,
CH(CH3)2), 26.1 (s, C6/C6H11), 27.8 (d, 3JCP ¼ 10 Hz, C4,5/C6H11), 28.0
(d, 3JCP ¼ 11 Hz, C4,5/C6H11), 29.3 (s, C2,3/C6H11), 29.8 (s, C2,3/C6H11),
30.3 (CH(CH3)2), 40.0 (d, 1JCP ¼ 20 Hz, C1/C6H11), 69.9 (d, 3JCP ¼ 7 Hz,
Cb/C5H4P), 72.1 (d, 2JCP ¼ 9 Hz, Ca/C5H4P), 72.7 (s, Ci/C5H4Si), 73.4 (s,
5732 (Rint ¼ 0.0299), R1 ¼ 0.0447, wR2 ¼ 0.1229 [I > 2
s(I)].
Acknowledgment
We are grateful to the Fonds der Chemischen Industrie for
generous financial support. J.J. and D.S. thank the Fonds der
Chemischen Industrie for Chemiefonds fellowships.
C5H4Si), 74.1 (s, C5H4Si), 82.1 (d, JCP ¼ 30 Hz, Ci/C5H4P), 85.1 (s,
1
C6H4), 89.6 (s, C6H4), 93.8 (s, Ci/C6H4), 106.7 (s, Ci/C6H4). 29Si{1H}
NMR (49.66 MHz, CDCl3,
(101.25 MHz, CDCl3,
d
): ꢀ2.8 (s, Si), 0.6 (s, Sicore). 31P{1H} NMR
d
): 16.3 (s).
Appendix A. Supplementary material
CCDC 903832 contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
Synthesis of Si(Fe(
C4H2O)2)RuCl2(
6-p-cymene)2)4 (11c)
h h
5-C5H4SiMe2(CH2)3)( 5-C5H4P(2-(5-Me)
h
Phosphine 3c (490 mg, 0.25 mmol) was reacted with 8 (310 mg,
0.51 mmol) as described earlier. After appropriate work-up, com-
plex 11c was obtained as a red solid. Yield: 760 mg (0.24 mmol, 95%
based on 3c). Anal. calcd. for C140H176Cl8Fe4O8P4Ru4Si5 (3162.50 g/
mol): C, 53.17; H, 5.61. Found: C, 53.09; H, 5.87. Mp.: 133 ꢁC. IR
Appendix B. Supporting information
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jorganchem.2015.02.036.
(NaCl,
y
~/cmꢀ1): 798/832 (m, SieC), 1024 (s, CeOeC), 1248 (m,
SieMe), 1592 (m, C]C), 2917/2958 (m, CeH). 1H NMR (500.3 MHz,
CDCl3, d
): 0.12 (s, 24H, H4/CH3), 0.45 (m, 8H, H1/CH2), 0.61 (m, 8H,
References
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1.85 (s, 12H, CH3), 2.45 (s, 24H, 5-CH3C4H2O), 2.73 (sept,
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C
{1H} NMR (125.81 MHz, CDCl3,
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CH3C4H2O), 17.3 (s, C1/CH2), 17.3 (s, CH3), 18.6 (s, C2/CH2), 21.5 (s, C3/
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C5H4P), 72.4 (s, Ci/C5H4Si), 73.0 (d, JCP ¼ 12 Hz, Ca/C5H4P), 74.0 (s,
2
Ca/C5H4Si), 74.1 (s, Cb/C5H4Si), 74.6 (d, 1JCP ¼ 55 Hz, Ci/C5H4P), 85.5
2
2
(d, JCP ¼ 6 Hz, C6H4), 90.8 (d, JCP ¼ 5 Hz, C6H4), 94.5 (s, Ci/C6H4),
106.9 (d, JCP ¼ 7 Hz, C4/5-MeC4H2O), 108.7 (s, Ci/C6H4), 124.1 (d,
3
2JCP ¼ 15 Hz, C3/5-MeC4H2O), 144.8 (d, 1JCP ¼ 74 Hz, C2/5-MeC4H2O),
156.4 (d, JCP ¼ 4 Hz, C5/5-MeC4H2O). 29Si{1H} NMR (49.66 MHz,
3
CDCl3,
CDCl3,
d
): ꢀ3.2 (s, Si), 0.5 (s, Sicore). 31P{1H} NMR (101.25 MHz,
d
): ꢀ3.8 (s).
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