Silylative coupling of terminal alkynes with iodosilanes: New catalytic activation of sp-hybridized carbon-hydrogen bonds

Article abstract of DOI:10.1021/om200038r

The [{Ir(μ-Cl)(CO)₂}₂] (I)-catalyzed reaction of terminal alkynes and diynes with Me₃SiI with the aid of NEt(i-Pr)₂ occurs smoothly, leading to the formation of mono- and bis-silyl-functionalized alkynyl derivat

Full text of DOI:10.1021/om200038r

ARTICLE
pubs.acs.org/Organometallics
Silylative Coupling of Terminal Alkynes with Iodosilanes: New
Catalytic Activation of sp-Hybridized CarbonꢀHydrogen Bonds
Ireneusz Kownacki, Bogdan Marciniec,* Beata Dudziec, and Maciej Kubicki
Department of Organometallic Chemistry, Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznan, Poland
S Supporting Information
b
ABSTRACT: The [{Ir(μ-Cl)(CO)2}2] (I)-catalyzed reaction
of terminal alkynes and diynes with Me3SiI with the aid of
NEt(i-Pr)2 occurs smoothly, leading to the formation of mono-
and bis-silyl-functionalized alkynyl derivatives. This new reaction, which occurs via direct activation of the CspꢀH bond in the
starting alkyne, is a very efficient and easy tool for the synthesis of unique silylated alkynes. Separate experiments of the equimolar
reactions of the precursor (I) with selected reaction substrates provided the evidence for the sequence reactions as well as for the real
catalyst to be [IrI(CO)(NEt(i-Pr)2)2].
Scheme 1. Ruthenium-Catalyzed Silylative Coupling of
Terminal Alkynes with Vinyl-Substituted Organosilicon
Compounds
’ INTRODUCTION
Organofunctionalized alkynylsilanes are important synthons of
alkynyl carboanions for the synthesis of organic and natural
products1 as well as precursors of optoelectronic materials.2 They
are usually prepared by classical methods of synthesis with employ-
ment of organometallic reagents3 and more recently by zinc salt-
mediated silylation of terminal alkynes with aminosilanes,4a
chlorosilanes,4b and Me3SiOTf4c (OTf = ꢀO3SCF3) as well as
by TM-catalyzed dehydrogenative silylation of terminal alkynes
with hydrosilanes4d (by [Ir4(CO)12]/PPh3 system) and cross-
metathesis offunctionalizedalkynes.4e Recently, we have reported a
method for the preparation of alkynylsilanes via silylative cross-
coupling of selected terminal alkynes with various vinylsilanes
catalyzed by complexes containing [Ru]ꢀH and/or [Ru]ꢀSi
bonds and occurring according to the following equation
(Scheme 1).5
Unfortunately, the silylation of phenylethyne with vinylsilane
does not take place because of the concurrent dimerization of the
initial alkyne preferred under the conditions of catalysis. Vinylsi-
licon compounds in this reaction act as silylating agents and
hydrogen acceptors. For general mechanistic implications see
a recent review.6
a representative reagent system. The reaction was found to
proceed efficiently in the presence of a catalytic system consisting
of iridium(I) chlorocarbonyl complex [{Ir(μ-Cl)(CO)2}2] (I)
and NEt(i-Pr)2 as a hydrogen iodide acceptor, leading to the
formation of appropriate silyl-substituted alkynyl derivatives and
evolution of ammonium salt according to Scheme 2 (Table 1).
Surprisingly, other very popular iridium(I) complexes appeared
to be unselective ([{Ir(μ-Cl)(cod)}2]) or even inactive ([Ir-
(Cl)(cod)(PCy3)], trans-[Ir(Cl)(CO)(PPh3)2], trans-[Ir(Cl)(CO)-
(PCy3)2]) in this reaction. The process of optimization of
the reaction conditions showed that other parameters, not only
the type of catalyst but also the types of amine and solvent, had a
strong influence on the selectivity and yield of the products
formed. Catalytic tests performed for the model substrate system,
i.e., phenylacetylene and Me3SiI, proved that a too low reaction
temperature and too low loading of the iridium catalyst do not
give acceptable yields of the desired product. As follows from
the results obtained for this reaction at different temperatures, i.e.,
80 and 110 °C, a definitely higher conversion as well as yield
of the target compound was observed for the process led at 80 °C.
We suppose that side processes occurring in the catalytic system
at higher temperature, e.g., dimerization and trimerization of
the initial alkyne (see Table 1), effectively deactivate catalytically
active iridium species. Moreover, lower efficiency of the process
studied at a higher temperature can also be caused by thermal
Most of the above-mentioned methods have many drawbacks
and limitations, in particular intolerance to functional groups
such as ꢀOH, ꢀNH2, ꢀC(O)ꢀ, ꢀNdCRꢀ, or (ꢀC(O))2NR
present in the substituents bonded to the Csp moiety. Therefore,
in this paper we present a new catalytic reaction that is a coupling
of various terminal alkynes with iodotrimethylsilane catalyzed by
iridium(I) complexes in the presence of tertiary organic amine as
a hydrogen halogen acceptor.7
’ RESULTS AND DISCUSSION
A new horizon of this strategy is to extend the silylative agents
(over vinylsilanes) to SiꢀX derivatives with elimination of a
[base H]X adduct as a byproduct according to Scheme 2.
3
Various iridium(I) complexes were examined as catalysts of
the silylative coupling reaction of phenylacetylene with Me3SiI as
Received: January 17, 2011
Published: April 13, 2011
r
2011 American Chemical Society
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Scheme 2. Coupling of Terminal Alkynes with
Iodotrimethylsilane (Me3SiI)
According to the available crystallographic data for substituted
alkynes, the C1ꢀC2 distance of 1.212(17) Å supports its triple-
bond character. Similar bond lengths were found in our bissilyl-
functionalized diynes, 1.202(2) and 1.203(2) Å in 18, and in 17
these distances are in the range 1.197(3)ꢀ1.201(3) Å. In the
latter compound, there are two symmetry-independent mol-
ecules in the asymmetric part of the unit cell; the geometrical
features of both molecules are very similar.
Formation of the silyl-functionalized alkyne derivative as well
as the hydroamonium iodide, according to Scheme 2, suggests
that the reaction of terminal alkynes with Me3SiꢀI occurs
through the iridium-mediated CspꢀH bond activation in the
initial terminal alkyne/diyne molecule, and it seems to be a key
step of this new process.
The CꢀH bond activation of 1-alkynes by a transition-metal
catalyst constitutes one of the most important methods in the
preparation of enynes. Since the Glaser8a coupling of terminal
acetylenes under copper catalysis with oxidation to give butadiynes
and the Strauss8b nonoxidative variant of coupling were discovered,
many papers have been published dealing with the transition-metal-
catalyzed transformation of terminal alkynes via CspꢀH bond
activation, particularly with employment of Ru,9 Rh,10 and Pd11
complexes. Recently also complexes of Ni,10mꢀo,12 Cu,13 Au,14,13l
Co,15 and Fe16 have been reported to catalyze the reaction of
terminal alkynes via alkynyl CꢀH bond cleavage. In the field of
iridium-catalyzed transformations of terminal alkynes, Miyaura
et al. have reported that the iridium-catalyzed dimerization of
terminal alkynes involves the oxidative addition of alkyne to a
low-valent Ir complex, followed by insertion of an alternative alkyne
to given dimers.17 Also Carreira et al. reported the addition of TMS-
acetylene to various aldimines catalyzed by [{Ir(μ-Cl)(cod)}2],
which occurs by CspꢀH bond activation, leading to the corre-
sponding amine-alkynyl derivatives.18 The same conclusion was
drawn by Ishii19 and Toyota20 studying the activity of iridium
complexes in dimerization of terminal alkynes and co-coupling of
the terminus with internal alkynes.
Table 1. [{Ir(μ-Cl)(CO)2}2]-Catalyzed Silylative Coupling
of Phenylacetylene with Me3SiI: Optimization of the Reaction
Conditionsa
temp
conversion
[%]
yield
[%]
[PhCtCH]:[Ir] solvent
[°C]
base
1:10ꢀ2
1:10ꢀ2b
1:10ꢀ2
1:2 ꢁ 10ꢀ3
1:10ꢀ2
1:10ꢀ2
1:10ꢀ2
1:10ꢀ2
toluene
toluene
toluene
toluene
toluene
toluene
THF
60
80
NEt(i-Pr)2
NEt(i-Pr)2
NEt(i-Pr)2
NEt(i-Pr)2
NEt3
36
97
85
21
68
0
36
97
76(9)c
21
110
80
80
68
80
C5H5N
0
80
NEt(i-Pr)2
68
68
DMF
80
NEt(i-Pr)2
83
83
a Reaction conditions: [Me3SiI]:[NEt(i-Pr)2] = 1.6:1.8, 24 h. b 12 h,
closed system. Conversion and yield were determined by GC analysis.
Decane was used as internal standard. c The target compound formation
was accompanied with dimerization and trimerization products of the
initial alkyne.
instability of species IV (see Scheme 4). Further tests performed
for other exemplary amines proved that less hindered amines
efficiently block catalytic activity of the initial iridium complex (see
Table 1). In addition, in this reaction, more polar solvents
containing in their structure donating heteroatoms suppress
effectively the activity of the iridium(I) catalytic system used. On
the basis of the data collected in Table 1, the iridium(I) binuclear
complex [{Ir(μ-Cl)(CO)2}2] with NEt(i-Pr)2 was chosen for
further study of this reaction.
Silylative coupling of selected alkynes, i.e., alkyl, cycloalkyl,
silyl, aryl as well as H2N- or HO-functionalized alkynes with
iodotrimethylsilane catalyzed by the precursor [{Ir(μ-Cl)-
(CO)2}2] (I) under the optimum conditions gives the respective
alkynylsilane exclusively (1ꢀ13) (see the data presented in
Table 2). Most of the new silyl-alkynyl derivatives were isolated
and fully characterized by spectroscopic methods (see the
Supporting Information). The method developed seems to be
universal, because it can be utilized efficiently for silylation of not
only nonfunctionalized alkynes. This iridium(I) catalytic system
appeared to be resistant to the initial ethyne derivatives contain-
ing reactive functionalities, such us ꢀOH and ꢀNH2, which in
the first step are O- or N-silylated by the appropriate equivalent of
Me3SiCl or Me3SiI and further coupled with Me3SiI (see the
Supporting Information).
It is worth emphasizing that the silylation of terminal diynes by
iodotrimethylsilane (see Table 3) gives exclusively and mostly
quantitatively bissilyl derivatives (14ꢀ18), which confirms the
advantages of this method over the coupling of terminal alkynes
with vinylsilanes catalyzed by ruthenium complexes5 as well as
other methods.1,4
All new bissilyl-functionalized diynes were isolated and fully
characterized by spectroscopic methods (see the Supporting
Information), and the structures of compounds 17 and 18 have
been solved by an X-ray method (Figures 1 and 2).
On the basis of the study of iridium-catalyzed cross-coupling of
the terminus with internal alkynes, Ishii19 proposed the reaction
mechanism based on the spectroscopic determination of the struc-
tures of the catalytically obtained products using Csp deuterium-
labeled phenylacetylene, whereas the mechanism we propose in
this paper is based on a series of experiments involving the
equimolar reactions of the precursor l with initial substrates.
Direct reaction of precursor l with model silylethyne
((i-Pr)3SiCtCH) in the presence of pyridine enabled us to
isolate six-coordinate iridium(III) complex IIIa. Formation of
such alkynyl-hydrydo iridium(III) complexes as products of
various terminal alkynes' oxidative addition to [Ir(η2-acac)-
(PPh3)2] has been previously reported by Oro.21 The iridium-
1
(III) organometallic species IIIa was fully characterized by H
and 13C NMR spectroscopy. In the 1H NMR spectrum, the lines
at 9.42 (dm), 6.68 (dtt), and 6.37 (dtm) ppm were assigned to
two pyridine ligands bonded to the iridium center. The reso-
nance lines at 1.28 (s) and 1.26 (s) assigned to i-Pr groups at
silicon, the singlet in the hydride region at ꢀ17.54 ppm, and the
lines at 100.01 and 97.24 ppm in the 13C NMR spectrum,
assigned to an ethynyl moiety, unambiguously confirmed the
formation of the silylethynyl-hydride complex IIIa via CspꢀH
bond activation in the initial silylethyne, according to Scheme 3.
The structure of complex IIIa was also solved by X-ray analysis,
giving direct evidence of activation of the CspꢀH bond by an
iridium(I) carbonyl complex.
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Table 2. Iridium(I)-Catalyzed Silylation of Terminal Alkynesa
a Reaction conditions: [alkyne]:[Me3SiI]:[NEt(i-Pr)2]:[Ir] = 1:1.6:1.8:10ꢀ2, 80 °C. b [alkyne]:[Me3SiI]:[NEt(i-Pr)2]:[Ir] = 1:1.6:1.8:(2 ꢁ 10ꢀ2), 80
°C. c [alkyne]:[Me3SiI]:[NEt(i-Pr)2]:[Ir] = 1:3.8:4.2:(2 ꢁ 10ꢀ2), 80 °C. The reactions were performed in a closed system. [Ir] = [{Ir(µ-Cl)(CO)2}2].
Toluene was used as a solvent: 8 mL for runs 1ꢀ11; 18 mL for runs 12 and 13. Conversion and yield were determined by GC analysis and calculated
using solvent as a standard.
The coordination number of the iridium atom is 6, and the
geometry of the coordination is close to that of a distorted
octahedron. The position of the hydrogen atom connected with
iridium was found in the difference Fourier map and is consistent
with both chemical arguments and the data from the Cambridge
Structural Database. In version 5.31 (November 2009 updated
August 2010) there are 676 examples of structures with an IrꢀH
bond, and more than a half of them (387) have the coordination
number 6. The IrꢀH distances have a mean value of 1.59 Å,
consistent with the length of 1.58 Å found in the present
structure. The C1ꢀC2 distance of 1.212(17) Å supports its
triple-bond character.
As shown in Figure 3, hydride and (i-Pr)3SiCtC ligands
occupy the cis position, while the chloride ligand occupies
the trans position in relation to the ethynyl ligand and the cis
position to the hydride ligand. Such a spatial configuration of the
ligands attached to the iridium center allows further steps, i.e.,
dehydrohalogenation of complex III by tertiary amine and
formation of iridium ethynyl species IV in the catalytic cycle
(Scheme 4).
A separate experiment of the equimolar reaction of precursor I
with HCtCSi(i-Pr)3 but in the presence of not only amine
(NEt(i-Pr)2) but also iodosilane (monitored by GC-MS and
NMR techniques) provided evidence of the sequence reactions
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Table 3. Iridium(I)-Catalyzed Silylation of Diynesa
a Reaction conditions: [diyne]:[Me3SiI]:[NEt(i-Pr)2]:[Ir] = 1:3.4:3.6:4 ꢁ 10ꢀ2, 80 °C. The reactions were performed in a closed system.
[Ir] = [{Ir(μ-Cl)(CO)2}2]. Toluene was used as a solvent: 6 mL for runs 4ꢀ18. Conversion and yield were determined by GC analysis and
calculated using solvent as a standard.
Figure 1. Perspective view of one of the molecules of 17 with atom
labeling. Ellipsoids are drawn at the 33% probability level; hydrogen
atoms are shown as spheres of arbitrary radii. Selected geometrical
parameters (distances, Å; angles, deg; the values for the second
symmetry-independent molecules are given in square brackets):
are shown as spheres of arbitrary radii. Selected geometrical parameters
Figure 2. Perspective view of one of the molecules of 18 with atom
labeling. Ellipsoids are drawn at the 33% probability level; hydrogen atoms
Si1ꢀC11 1.850(3) [1.850(3)], Si1ꢀC21 1.862(2) [1.862(3)],
Si1ꢀC31 1.836(2) [1.831(2)], C31ꢀC32 1.197(3) [1.201(3)],
C32ꢀSi3 1.841(2) [1.841(2)], Si1ꢀC41 1.830(2) [1.834(2)],
C41ꢀC42 1.196(3) [1.200(3)], C42ꢀSi4 1.845(3) [1.842(2)], Si1ꢀ
C31ꢀC32 178.7(2) [174.1(2)], C31ꢀC32ꢀSi3 176.6(3) [177.7(3)],
Si1ꢀC41ꢀC42 177.5(3) [176.3(2)], C41ꢀC42ꢀSi4 178.2(3)
[178.1(3)].
(distances, Å; angles, deg): Si1ꢀC11 1.831(2), Si1ꢀC21 1.828(2),
Si1ꢀC31 1.866(2), Si1ꢀC41 1.864(2), C11ꢀC12 1.202(2), C21ꢀC22
1.203(2), Si1ꢀC11ꢀC12 178.3(2), C11ꢀC12ꢀSi13 178.9(2), Si1ꢀ
C21ꢀC22 176.7(2), C21ꢀC22ꢀSi23 177.3(2).
elimination leads to formation of appropriate silylethyne and
regeneration of the tetracoordinated IrI complex II (Scheme 5).
The latter II appeared to be the catalytically active species of the
cycle illustrated in Scheme 4. The singlet at ꢀ19.66 ppm assigned
to the[Ir]-Hmoietyinthe1H NMR spectrum recorded to monitor
the reaction of precursor I with HCtCSi(i-Pr)3 and NEt(i-Pr)2 at
of oxidative addition of alkynes, followed by the elimination of
ammonium chloride to form complex IV and subsequent oxida-
tive addition of iodosilane to get complex V. Its reductive
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Scheme 3. Activation of a HꢀCsp Bond: A Key Step of the Mechanism
Scheme 4. Mechanism Proposed for the Silylative Coupling
of Terminal Alkynes with Me3SiI
Figure 3. X-ray structure of the species IIIa. Selected geometrical
parameters (distances, Å; angles, deg): Ir1ꢀCl1 2.412(3), Ir1ꢀN21
2.119(8), Ir1ꢀN15 2.201(11), Ir1ꢀC13 1.827(17), Ir1ꢀC1 1.969(15),
Ir1ꢀH1 1.58, C1ꢀC2 1.212(17), C13ꢀO14 1.148(17), C13ꢀIr1ꢀ
N21 171.2(5), C1ꢀIr1ꢀCl1 171.9(3), N15ꢀIr1ꢀH1 158, Ir1ꢀC1ꢀ
C2 176.9(11), Ir1ꢀC13ꢀC14 178.2(16).
Varian Gemini 300 VT and Varian Mercury 300 VT spectrometers in
benzene-d6 and CDCl3.
The chemicals were obtained from the following sources: IrCl3 3H2O
50 °C as well as the lines at 98.99 and 95.23 ppm in 13C NMR
spectrum assigned to the (i-Pr)3SiCtC ligand confirm the forma-
tion of complex III, which at higher temperatures and in an excess
of organic base (tertiary amine) gives complex IV. Formation of
the latter species is confirmed by the appearance of new lines
at 94.21 and 90.83 in the 13C NMR spectrum, assigned to
(i-Pr)3SiCtC-[Ir] species, and by the disappearance of the singlet
at ꢀ19.66 ppm in 1H NMR spectrum after the reaction at 80 °C.
Addition of ISiMe3 leads to complex V, which in the next step is
transformed to complex II with evolution of 1-triisopropylsilyl-2-
trimethylsilylethyne (confirmed by GC-MS analysis).
3
from Pressure Chemicals; cod, PPh3, PCy3, C6D6, CDCl3, DMF, THF,
decane, C5H5N, NEt3, NEt(i-Pr)2, Me3SiI, toluene from Aldrich; CO from
Linde Gas. The complexes [{Ir(μ-Cl)(cod)}2],22 [Ir(Cl)(cod)(PCy3)],23
trans-[Ir(Cl)(CO)(PPh3)2],24 [Ir(Cl)(CO)(PCy3)2],25 and [{Ir(μ-Cl)-
(CO)2}2]26 were synthesized according to the published methods. All
solvents and liquid reagents were dried and distilled under argon prior to use.
General Procedure for Catalytic Tests. The glass Schlenk
reactor (10 mL) equipped with a magnetic stirring bar was evacuated
and flushed with argon. The calculated amount of the complex [{Ir(μ-
Cl)(CO)2}2] (0.005 or 0.0025 mmol) was placed in the reactor in the
flow of argon; then 3 mL of solvent and a calculated amount of amine
(1.8 mmol) wereadded. The mixtureobtainedwasstirredforabout 10min.
In the next step, appropriate amounts of phenylacetylene (0.102 g, 1 mmol),
Me3SiI (0.32 g, 1.6 mmol), and decane (5% of initial mixture volume) were
added, and the reaction was conduced at the given temperature. The
reaction mixture was analyzed by GC and GC-MS at the beginning and after
24 h. Conversion and yield were calculated using the internal standard
calculation method.
General Procedure for Silylation of Terminal Alkynes. The
glass Schlenk reactor equipped with a magnetic stirring bar was
evacuated and flushed with argon. The calculated amount of the complex
[{Ir(μ-Cl)(CO)2}2] was placed in the reactor in the flow of argon; then
toluene and a calculated amount of NEt(i-Pr)2 were added. The mixture
obtained was stirred for 10 min. In the next step, appropriate amounts of
terminal alkyne or diyne and Me3SiI were added. The reaction was
conducted in a closed system at 80 °C upon stirring, until the full
conversion of initial alkyne/diyne. After the reaction completion,
toluene and the excess of other reagents were evaporated under reduced
pressure. The crude product was isolated by purification on the SiO2
column with hexane as eluent.
’ CONCLUSIONS
In conclusion, we have described a novel catalytic route for the
activation of CspꢀH bonds via the silylative coupling of terminal
(also carbon functionalized) alkynes and diynes by iodotri-
methylsilane in the presence of [{Ir(μ-Cl)(CO)2}2] as a catalyst
precursor. This new reaction under optimum conditions appears
to be a very efficient and easy method for the synthesis of novel
and unique mono- or multisilylated alkynes, which might be used
as building blocks for construction of molecular and macromo-
lecular organic compounds with precisely dedicated chemical,
electronic, and optoelectronic properties.
’ EXPERIMENTAL SECTION
General Methods and Chemicals. All synthesis and manipula-
tions were carried out under argon using standard Schlenk-line and
vacuum techniques. 1H, 13C, and 29Si NMR spectra were recorded on
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Scheme 5. Transformation of the Initial Iridium(I) Precursor
Synthesis of [Ir(Cl)(CO)(H)(CtCSi(i-Pr3))(py)2] (IIIa). Pyri-
dine (0.316 g, 4.00 mmol) was introduced into a vigorously stirred
suspension of [{Ir(μ-Cl)(CO)2}2] (0.284 g, 0.5 mmol) in 5 mL of
toluene at room temperature under a dry argon atmosphere over
10 min; then to the yellow solution obtained was added HCtCSi-
(i-Pr)3 (0.218 g, 1.2 mmol). The reaction was conducted for 24 h at
80 °C. After this time the content was cooled to room temperature.
Subsequently, the reaction mixture was filtered off by a cannula system,
then the solvent was removed under reduced pressure, and pentane was
added. The white suspension obtained was washed with pentane by
decantation. Yield: 0.536 g (90%).
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1H NMR (300 MHz, C6D6, 300 K): δ (ppm) 9.42 (dm), 6.68 (dtt),
6.37 (dtm) (10 H, C5H5N); 1.28 (s), 1.26 (s) (21H, i-Pr); ꢀ17.54 (s,
1H, Ir-H). 13C NMR (75.42 MHz, C6D6, 300 K): δ (ppm) 163.42
(CO); 153.58, 151.66, 138.05, 137.94, 125.08, 124.47 (C5H5N), 100.01,
97.24 (CtCSi(i-Pr)3); 19.36 (Me); 12.62 (CHMe2). 29Si NMR (59.59
MHz, C6D6, 300 K): δ (ppm) ꢀ6.48 (Si(i-Pr)3).
Sequential Stoichiometric Reaction of Precursor I with
(i-Pr)3SiCtCH, NEt(i-Pr)2, and ISiMe3. A portion of NEt(i-Pr)2
(0.168 g, 1.3 mmol) was introduced into a vigorously stirred suspension of
[{Ir(μ-Cl)(CO)2}2] (0.0738 g, 0.13 mmol) in 0.6 mL of benzene-d6 in a
Young NMR tube at room temperature under a dry argon atmosphere.
After 30 min to the yellow solution obtained was added HCtCSi(i-Pr)3
(0.0766 g, 0.387 mmol). The reaction was carried out for 3 h at 50 °C. After
NMR analysis the reaction was continued for 18 h at 80 °C. Afterward, to
the dark red solution was added 0.078 g (0.39 mmol) of ISiMe3. The
reaction was monitored by NMR and GC-MS techniques.
Crystallography. For crystal data, data collection, and structure
refinement see the Supporting Information.
Crystallographic data (excluding structure factors) for the structural
analysis have been deposited with the Cambridge Crystallographic Data
Centre, Nos. CCDC-762977 (IIIa), CCDC-806590 (17), and CCDC-
806591 (18). Copies of this information may be obtained free of charge
from The Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK.
Fax: þ44(1223)336-033, e-mail:deposit@ccdc.cam.ac.uk, or www:
www.ccdc.cam.ac.uk.
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’ ASSOCIATED CONTENT
S
Supporting Information. This material is available free
b
of charge via the Internet at http://pubs.acs.org.
’ AUTHOR INFORMATION
Corresponding Author
*Tel: þ48 061 8291366. Fax: þ48 061 8291508. E-mail: bogdan.
marciniec@amu.edu.pl.
’ ACKNOWLEDGMENT
(10) (a) Singer, H.; Wilkinson, G. J. Chem. Soc. (A) 1968, 849.
(b) Schmitt, H. J.; Singer, H. J. Organomet. Chem. 1978, 153, 165.
(c) Schafer, H.; Marcy, R.; Ruping, T.; Singer, H. J. Organomet. Chem.
This work was made possible by grant no. N 204 443840 from
the Ministry of Science and Higher Education.
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